Methods for coating semiconductor nanocrystals

ABSTRACT

A coated quantum dot and methods of making coated quantum dots are provided. Products including quantum dots described herein are also disclosed.

This application is a continuation of International Application No.PCT/US2012/066145, filed 20 Nov. 2012, which was published in theEnglish language as International Publication No. WO 2013/078247 on 30May 2013, which International Application claims priority to U.S.Provisional Patent Application No. 61/562,463, filed on 22 Nov. 2011,U.S. Provisional Patent Application No. 61/636,701, filed on 22 Apr.2012, and U.S. Provisional Patent Application No. 61/678,883, filed on 2Aug. 2012. Each of the foregoing is hereby incorporated herein byreference in its entirety for all purposes.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to semiconductor nanocrystals, alsoreferred to as quantum dots, methods of coating or providing layers onquantum dots, and products including same.

SUMMARY OF THE INVENTION

The present invention relates to quantum dots including an overcoating,methods for overcoating quantum dots, materials and products includingquantum dots taught herein, and materials and products including quantumdots made by a method taught herein.

In accordance with one aspect of the present invention, there isprovided a method of forming one or more coatings or layers or shells onquantum dots wherein amine species are not present or are notsubstantially present during formation of at least the outermost coatingor layer or shell on core quantum dots.

Preferably, one or more of the coatings or layers or shells are formedat a high temperature (e.g., >240° C.).

A quantum dot that is coated by a method taught herein may also bereferred to as a “core” particle or a “core” quantum dot.

In certain embodiments, the core particle on which a coating or layer orshell is to be formed is substantially free of amine species.

In certain embodiments including a core quantum dot including an aminespecies, the amine species can be removed or substantially removed fromthe core quantum dots prior to providing a coating or layer or shell onthe core quantum dots, whether the reactants producing the coating orlayer or shell do or do not include amine species.

In accordance with another aspect of the present invention, there isprovided a method of providing two or more coatings on a quantum dot,the method comprising forming a first coating or layer or shellcomprising zinc chalcogenide on a quantum dot core to form first coatedquantum dots, and forming a second coating comprising a semiconductormaterial on first coated quantum dots, wherein the second coating isformed in the substantial absence of amine species.

In certain embodiments, the first coating is formed in the substantialabsence of amine species.

A shell comprising zinc chalcogenide can comprise zinc sulfide, zincselenide, or other zinc chalcogenide, or a mixture including at leastone of the foregoing.

Preferably, one or more of the coatings or layers or shells are formedat a high temperature (e.g., >240° C.).

In one example, the method comprises providing a first reaction mixtureincluding core quantum dots, a zinc carboxylate and one or morechalcogen sources at a temperature of greater than 240° C. , preferablygreater than 280° C.; forming a first coating from the zinc carboxylateand one or more chalcogen sources on at least a portion of the corequantum dots to form first coated quantum dots; forming a secondreaction mixture comprising one or more metal carboxylates, one or morechalcogen sources, and first coated quantum dots at a temperature ofgreater than 240° C. , preferably greater than 280° C., in thesubstantial absence of an amine species; and forming a second coating onthe first coated quantum dots from one or metal carboxylate(s) and oneor more chalcogen sources.

Preferably, the first coating comprising one or more zinc chalcogens isformed in the substantial absence of an amine species.

In certain embodiments, the second coating comprises Cd_(X)Zn_(1-X)Swherein 0<x<1.

In certain embodiments of the method wherein the second coatingcomprises Cd_(X)Zn_(1-X)S wherein 0<x<1, the total molar equivalents ofchalcogen included in the one more chalcogen sources included in thesecond reaction mixture and total molar equivalents of metal included inthe one or more metal carboxylate sources included in the secondreaction mixture are included in a ratio of total molar equivalents ofchalcogen to total molar equivalents of metal in a range from greaterthan 1 to 4.

In one example, the method comprises providing a first reaction mixtureincluding core quantum dots, a zinc carboxylate and a sulfur source at atemperature of greater than 240° C. , preferably greater than 280° C.;forming a first coating from the zinc carboxylate and sulfur source onat least a portion of the core quantum dots to form first coated quantumdots; forming a second reaction mixture comprising one or more metalcarboxylates, one or more chalcogen sources, and first coated quantumdots at a temperature of greater than 240° C. , preferably greater than280° C., in the substantial absence of an amine species; and forming asecond coating on the first coated quantum dots from one or more metalcarboxylate(s) and one or more chalcogen sources.

Preferably, the first coating comprising zinc sulfide is formed in thesubstantial absence of an amine species.

In another example, the method comprises providing a first reactionmixture including core quantum dots, a zinc carboxylate and a seleniumsource at a temperature of greater than 300° C. , preferably greaterthan 310° C.; forming a first coating from the zinc carboxylate andselenium source on at least a portion of the core quantum dots to formfirst coated quantum dots; forming a second reaction mixture comprisingone or more metal carboxylates, one or more chalcogen sources, and firstcoated quantum dots at a temperature of greater than 240° C. ,preferably greater than 280° C., in the substantial absence of an aminespecies; and forming a second coating on the first coated quantum dotsfrom one or more metal carboxylate(s) and one or more chalcogen sources.

Preferably, the first coating comprising zinc selenide is formed in thesubstantial absence of an amine species.

In certain embodiments, the core particle on which a coating or layer orshell is to be formed is substantially free of amine species.

In certain embodiments including a core quantum dot including an aminespecies, the amine species can be removed or substantially removed fromthe core quantum dots prior to providing a coating or layer or shell onthe core quantum dots, whether the reactants producing the coating orlayer or shell do or do not include amine species.

According to an additional aspect of the present invention, there isprovided a quantum dot including a core particle having a first coatingor layer or shell comprising zinc chalcogenide (e.g., zinc sulfide, zincselenide, or other zinc chalcogenide, or a mixture including at leastone of the foregoing) on an outer surface of the core particle, and asecond coating comprising a semiconductor material disposed over thefirst coating wherein the second coating is substantially free of aminespecies.

In certain embodiments, the first coating, layer or shell on a coreparticle is substantially free of amine species.

In certain embodiments, the coating, layer or shell on a core particleis substantially free of amine species at the surface of the coating,layer or shell whether the amine species is free, unreacted or unboundor as bound ligands.

In certain embodiments, the quantum dot can have a solid statephotoluminescence external quantum efficiency at a temperature of 90° C.or above that is at least 95% of the solid state photoluminescenceexternal quantum efficiency of the semiconductor nanocrystal at 25° C.In certain embodiments, the temperature of 90° C. or above is above 100°C., In certain embodiments the temperature is in a range, for example,from 90° C. to about 200° C., from 90° C. to about 140° C., from 90° C.to about 120° C., or from 90° C. to about 100° C.

In certain embodiments, the quantum dot can have a solid statephotoluminescence efficiency at the temperature of 90° C. or above whichis from 95 to 100% of the solid state photoluminescence efficiency at25° C.

In applications where quantum dots are included or embedded within ahost material (e.g., a matrix), and in which the quantum dot-hostmaterial system which will be subjected to light flux, e.g., in excessof 1 W/cm², discoloration of the host material can be accelerated whenthe matrix is at a temperature >100° C. While not wishing to be bound bytheory, the presence of amines is believed to increase the probabilityof unwanted photochemistry at such light flux levels which can result indiscoloration of the host material. In addition, the curing mechanismof, for example, some silicone matrices using a Pt catalyst can bedeactivated by the presence of amines Accordingly, one aspect of thepresent invention is to synthesize quantum dots that are substantiallyfree of amine species in either the core particle or coating or layer orshell or both.

According to another aspect of the present invention, the absence orsubstantial absence of amine species in the coating or layering orshelling process of quantum dots advantageously reduces, inhibits orlowers yellowing, browning or discoloration of a matrix including suchquantum dots when the matrix is placed under light flux conditions,e.g., in excess of 1 Watt (W)/square centimeter (cm²), whichdiscoloration can be accelerated when the matrix is at atemperature >100° C.

According to an additional aspect, the absence or substantial absence ofamine species in the core particles whether as bound ligands or as free,unreacted or unbound amine species prior to providing a coating or layeror shell on the core quantum dots and where the reactants producing thecoating or layer or shell do not include amine species, results inquantum dot particles lacking or substantially lacking amine species.Such particles, when used in a matrix under light flux conditions, e.g.,in excess of 1 W/cm² and/or temperature conditions >100° C., forexample, advantageously inhibit, reduce or lower yellowing, browning ordiscoloration of the quantum dot matrix. Accordingly, certain aspects ofthe present invention are directed to quantum dot particles which lackor substantially lack amine species that otherwise would result indiscoloration or yellowing or browning when used in a matrix under lightflux conditions, e.g., in excess of 1 W/cm², which discoloration can beaccelerated when the matrix is at a temperature >100° C.

Exemplary methods of providing a core quantum dot with one or morecoatings, layers or shells are described herein. Exemplary methods ofproviding a core quantum dot with one or more coatings, layers or shellsare known to those of skill in the art. In an exemplary embodiment, ahigh temperature overcoating process is a process where a coating orlayer or shell is provided on the surface of a core quantum dot at atemperature of greater than 240° C., greater than 250° C., greater than260° C., greater than 270° C., greater than 280° C., greater than 290°C., greater than 300° C., greater than 310° C., or greater than 320° C.

According to certain aspects, a core quantum dot may be provided withone or more coatings or layers or shells of a same or differentmaterial. Selection of the materials for the one or more coatings orlayers or shells of the same or different material may be made to alterthe emitting characteristics of the resulting core-shell quantum dot.According to an additional aspect, a coating process is provided whichlacks or substantially lacks an amine species. According to this aspect,materials are selected which can be used to coat a core quantum dotparticle in the absence or substantial absence of an amine species.According to this aspect, a reaction mixture of core quantum dotparticles and coating reactants is provided which lacks an aminespecies. According to an additional aspect, a method of makingcore-shell quantum dots is provided which lacks an amine species in thereaction mixture used to form one or more coatings, layers or shells oncore quantum dot particles. The absence or substantial absence of anamine species during the coating process produces core-shell quantumdots which when used in a matrix under light flux, e.g., in excess of 1W/cm² and/or temperature conditions >100° C., inhibit, reduce or lowerdiscoloring or yellowing or browning.

Embodiments of the present invention are further directed to methods ofincreasing, improving or enhancing emission of quantum dots or otherwiseincreasing, improving or enhancing the lifetime of quantum dots.According to certain aspects, quantum dots are provided which lack orsubstantially lack amine species at least at the outer surface thereof.Core quantum dots are coated using a procedure which lacks amine speciesto result in core-shell quantum dots having increased, improved orenhanced emission and/or an increased, improved or enhanced lifetime.According to an additional aspect, materials for one or more coatings orlayers or shells are selected. A core quantum dot particle provided withone or more coatings or layers or shells of a same or different materialin the absence or substantial absence of an amine species results incore-shell quantum dots having increased, improved or enhanced emission.

In certain embodiments, quantum dots taught herein can have a solidstate EQE of at least 90%.

The core-shell quantum dots of the present invention may be present, forexample, in a matrix or host material and placed in capillaries whichare used, for example, in back light units. The quantum dots may also beused in films or solid state lighting applications or in any applicationutilizing quantum dots, such as direct on-chip semiconductor LEDapplications, electroluminescent applications such as QLEDs, solarapplications such as photovoltaic cells and concentrators, anddiagnostic and medical applications such as labeling, imaging and thelike.

In accordance with a still further aspect of the present invention,there is provided a composition including at least one quantum dotdescribed herein. In certain embodiments of the composition, the solidstate photoluminescence efficiency of the composition is at least 80% ata temperature of 90° C. or above. In certain embodiments of thecomposition, the solid state photoluminescence efficiency of thecomposition at a temperature of 90° C. or above is at least 95% of thesolid state photoluminescence efficiency of the composition at 25° C. Incertain embodiments, the temperature of 90° C. or above is above 100° C.In certain embodiments the temperature is in a range, for example, from90° C. to about 200° C., from 90° C. to about 140° C., from 90° C. toabout 120° C., or from 90° C. to about 100° C.

In certain embodiments, the composition further includes a hostmaterial.

In accordance with a still further aspect of the present invention,there is provided an optical material comprising at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided a light emitting material comprising at least onequantum dot described herein.

In accordance with a still further aspect of the present invention,there is provided an optical component including at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided a backlighting unit including at least one quantum dotdescribed herein.

In accordance with a still further aspect of the present invention,there is provided a display including at least one quantum dot describedherein.

In accordance with a still further aspect of the present invention,there is provided an electronic device including at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided an opto-electronic device including at least onequantum dot described herein.

In accordance with a still further aspect of the present invention,there is provided a light-emitting device including at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided a lamp including at least one quantum dot describedherein.

In accordance with a still further aspect of the present invention,there is provided a light bulb including at least one quantum dotdescribed herein.

In accordance with a still further aspect of the present invention,there is provided a luminaire including at least one quantum dotdescribed herein.

In accordance with yet another aspect of the present invention, there isprovided a population of quantum dots including at least on quantum dotdescribed herein. In certain embodiments, the light emitted by thepopulation has a peak emission at a predetermined wavelength with anFWHM less than about 60 nm. In certain embodiments, the FWHM is in arange from about 15 to about 50 nm.

In accordance with yet another aspect of the present invention, there isprovided a population of quantum dots prepared in accordance with any ofthe methods described herein. In certain embodiments, the light emittedby the population has a peak emission at a predetermined wavelength withan FWHM less than about 60 nm. In certain embodiments, the FWHM is in arange from about 15 to about 50 nm.

In accordance with a still further aspect of the present invention,there is provided a composition including at least one quantum dotprepared in accordance with any of the methods described herein. Incertain embodiments of the composition, the solid statephotoluminescence efficiency of the composition is at least 80% at atemperature of 90° C. or above. In certain embodiments of thecomposition, the solid state photoluminescence efficiency of thecomposition at a temperature of 90° C. or above is at least 95% of thesolid state photoluminescence efficiency of the composition at 25° C. Incertain embodiments, the composition further includes a host material.

In accordance with a still further aspect of the present invention,there is provided an optical material comprising at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a light emitting material comprising at least onequantum dot prepared in accordance with any of the methods describedherein.

In accordance with a still further aspect of the present invention,there is provided an optical component including at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a backlighting unit including at least one quantum dotprepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a display including at least one quantum dot preparedin accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided an electronic device including at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided an opto-electronic device including at least onequantum dot prepared in accordance with any of the methods describedherein.

In accordance with a still further aspect of the present invention,there is provided a light-emitting device including at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a lamp including at least one quantum dot prepared inaccordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a light bulb including at least one quantum dotprepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a luminaire including at least one quantum dotprepared in accordance with any of the methods described herein.

In certain embodiments of the various aspects and embodiments of theinventions described herein, the quantum dot core and shells areundoped.

In certain embodiments of the various aspects and embodiments of theinventions described herein, a quantum dot described herein can beincluded in a device, component, or product in the form of a compositionin which it is included.

In accordance with certain aspects, oxygen and/or water may degradesemiconductor nanocrystals or quantum dots described herein duringperiods of high light flux exposure.

The foregoing, and other aspects and embodiments described herein allconstitute embodiments of the present invention.

It should be appreciated by those persons having ordinary skill in theart(s) to which the present invention relates that any of the featuresdescribed herein in respect of any particular aspect and/or embodimentof the present invention can be combined with one or more of any of theother features of any other aspects and/or embodiments of the presentinvention described herein, with modifications as appropriate to ensurecompatibility of the combinations. Such combinations are considered tobe part of the present invention contemplated by this invention.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention as claimed. Other embodimentswill be apparent to those skilled in the art from consideration of thespecification and practice of the invention disclosed herein.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings,

FIG. 1A graphically illustrates the Absorption spectrum of the CdSe corereferred to in Example III; FIG. 1B graphically illustrates theabsorption and emission spectra of CdSe/ZnSe/CdZnS referred to inExample III.

FIG. 2A graphically illustrates the Absorption spectrum of the CdSe corematerial referred to in Example IV; FIG. 2B graphically illustrates theabsorption and emission spectra of CdSe/ZnS/CdZnS referred to in ExampleIV.

FIG. 3 graphically illustrates the effect of varying the Sulfur to Metalratio in the second shell overcoating preparation on the absorbancespectrum (normalized to the first excitonic features.)

FIG. 4 graphically illustrates the calculated EQE values as a functionof temperature for sample films prepared with the semiconductornanocrystals prepared generally in accordance with the proceduresdescribed in Examples III and IV.

FIG. 5 graphically illustrates integrated photoluminescence intensity asa function of temperature for sample films prepared with thesemiconductor nanocrystals prepared generally in accordance with theprocedures described in Examples III and IV.

FIGS. 6A and 6B graphically illustrate normalized integrated plots ofabsorption versus wavelength for semiconductor nanocrystals inaccordance with the present invention, prepared generally in accordancewith Examples III and IV.

FIG. 7A graphically illustrates the Absorption spectrum of the CdSe corematerial referred to in Example VIIA; FIG. 7B graphically illustratesthe absorption and emission spectra of the overcoated nanocrystalreferred to in Example VIM.

FIG. 8A graphically illustrates the Absorption spectrum of the CdSe corematerial referred to in Example VIIIA; FIG. 7B graphically illustratesthe absorption and emission spectra of the overcoated nanocrystalreferred to in Example VIIIB.

The attached figures are simplified representations presented forpurposes of illustration only; the actual structures may differ innumerous respects, particularly including the relative scale of thearticles depicted and aspects thereof.

For a better understanding to the present invention, together with otheradvantages and capabilities thereof, reference is made to the followingdisclosure and appended claims in connection with the above-describeddrawings.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention are directed to methods of makingor processing core quantum dots or quantum dots resulting in an absenceor substantial absence of amine species in the quantum dots at least atthe outer surface thereof. According to one aspect, core quantum dotswhich may or may not have an absence or substantial absence of aminespecies are provided thereon with one or more coatings or layers orshells of a same or different material in the absence or substantialabsence of an amine species to provide a core-shell quantum dot.According to a further aspect, core quantum dots having an absence orsubstantial absence of amine species are then provided with one or morecoatings or layers or shells of a same or different material to providea core-shell quantum dot in the absence or substantial absence of anamine species to provide a core-shell quantum dot.

Examples of amine species excluded from or substantially excluded fromthe methods and quantum dots taught herein include, but are not limitedto, amines, aliphatic primary amines such as oleyl amine, octylamine andthe like, aliphatic secondary amines such as dioctyl amine and the like,aliphatic tertiary amines such as trioctylamine and the like, andaromatic amines or semiaromatic amines such as pyridine, imidazole andthe like.

Quantum dots or nanocrystals are nanometer sized semiconductor particlesthat can have optical properties arising from quantum confinement.Quantum dots can have various shapes, including, but not limited to asphere, rod, disk, other shapes, and mixtures of various shapedparticles. The particular composition(s), structure, and/or size of aquantum dot can be selected to achieve the desired wavelength of lightto be emitted from the quantum dot upon stimulation with a particularexcitation source. In essence, quantum dots may be tuned to emit lightacross the visible spectrum by changing their size. See C. B. Murray, C.R. Kagan, and M. G. Bawendi, Annual Review of Material Sci., 2000, 30:545-610 hereby incorporated by reference in its entirety. The narrowFWHM of quantum dots can result in saturated color emission. The broadlytunable, saturated color emission over the entire visible spectrum of asingle material system is unmatched by any class of organic chromophores(see, for example, Dabbousi et al., J. Phys. Chem. 101, 9463 (1997),which is incorporated by reference in its entirety). A monodispersepopulation of quantum dots will emit light spanning a narrow range ofwavelengths.

Exemplary quantum dots include, for example, quantum dots comprising asemiconductor material that can be represented by the formula MX,wherein M represents one or more metals and X represents one or morechalcogens and/or one or more pnictogens. Such quantum dots can beformed from quantum dot precursors comprising one or more M donors andone or more X donors which are capable of reacting to form the desiredsemiconductor material. In certain embodiments, the M donor and the Xdonor can be moieties within the same molecule. The M donor can be aninorganic compound, an organometallic compound, or elemental metal. Forexample, an M donor can comprise cadmium, zinc, magnesium, mercury,aluminum, gallium, indium or thallium, and the X donor can comprise acompound capable of reacting with the M donor to form a material withthe general formula MX. Exemplary metal precursors include metalcarboxylates. Exemplary metal precursors include dimethylcadmium,cadmium oleate and zinc oleate. The X donor can comprise a chalcogenidedonor or source or a pnictide donor, such as a phosphine chalcogenide, abis(silyl)chalcogenide, dioxygen, an ammonium salt, or atris(silyl)pnictide. Suitable X donors include, for example, but are notlimited to, dioxygen, bis(trimethylsilyl)selenide ((TMS)₂Se), trialkylphosphine selenides such as (tri-noctylphosphine)selenide (TOPSe) or(tri-n-butylphosphine)selenide (TBPSe), trialkyl phosphine telluridessuch as (tri-n-octylphosphine)telluride (TOPTe) orhexapropylphosphorustriamide telluride (HPPTTe),bis(trimethylsilyl)telluride ((TMS)₂Te), bis(trimethylsilyl)sulfide((TMS)₂S), a trialkyl phosphine sulfide such as (tri-noctylphosphine)sulfide (TOPS), dialkyl phosphine selenide, aliphatic thiol, triethylphosphine sulfide, tributyl phosphine sulfide, sulfur-octadecene,selenium-octadecene, an ammonium salt such as an ammonium halide (e.g.,NH₄C1), tris(trimethylsilyl)phosphide ((TMS)₃P), tris(trimethylsilyl)arsenide ((TMS)₃As), or tris(trimethylsilyl)antimonide ((TMS)₃Sb). Incertain embodiments, the M donor and the X donor can be moieties withinthe same molecule.

A quantum dot can comprise one or more semiconductor materials. Examplesof semiconductor materials that can be included in a quantum dot(including, e.g., a semiconductor nanocrystal) include, but are notlimited to, a Group IV element, a Group II-VI compound, a Group II-Vcompound, a Group III-VI compound, a Group III-V compound, a Group IV-VIcompound, a Group I-III-VI compound, a Group II-IV-VI compound, a GroupII-IV-V compound, an alloy including any of the foregoing, and/or amixture including any of the foregoing, including ternary and quaternarymixtures or alloys. Examples of Group II elements include Zn, Cd, andHg. Examples of Group VI elements include oxygen, sulfur, selenium andtellurium. Examples of Group III elements include boron, aluminum,gallium, indium, and thallium. Examples of Group V elements includenitrogen, phosphorus, arsenic, antimony, and bismuth. Examples of GroupIV elements include silicon, germanium, tin, and lead.

A non-limiting list of examples include ZnO, ZnS, ZnSe, ZnTe, CdO, CdS,CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe,InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TlN, TlP, TlAs, TlSb, PbO,PbS, PbSe, PbTe, Ge, Si, an alloy including any of the foregoing, and/ora mixture including any of the foregoing, including ternary andquaternary mixtures or alloys.

In certain embodiments, quantum dots can comprise a core comprising oneor more semiconductor materials and a shell comprising one or moresemiconductor materials, wherein the shell is disposed over at least aportion, and preferably all, of the outer surface of the core. A quantumdot including a core and shell is also referred to as a “core/shell”structure.

For example, a quantum dot can include a core having the formula MX,where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium,thallium, or mixtures thereof, and X is oxygen, sulfur, selenium,tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof.Examples of materials suitable for use as quantum dot cores include, butare not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS,MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP,InSb, AlAs, AlN, AlP, AlSb, TlN, TlP, TlAs, TlSb, PbO, PbS, PbSe, PbTe,Ge, Si, an alloy including any of the foregoing, and/or a mixtureincluding any of the foregoing, including ternary and quaternarymixtures or alloys.

The X donor can comprise a chalcogenide donor where X is a chalcogenideincluding oxygen, sulfur, selenium, or tellurium, or mixtures thereof.Suitable chalcogenide donors include a reactive chalcogenide source,such as highly reactive chalcogenide sources such as (TMS)₂Se, (TMS)₂S,H₂S, chalcogenide mixtures such as octadecene-Se (ODE/Se), octadecene-S(ODE/S), amine-Se, amine-S and mixtures thereof and secondary phosphinechalcogenides such as a secondary phosphine sulfide, a secondaryphosphine selenide, a secondary phosphine telluride, or a secondaryphosphine oxide or mixtures thereof or dialkylphosphine chalcogenidessuch as diisobutylphosphine selenides, diisobutylphosphine sulfides,diphenylphosphine selenides or diphenylphosphine sulfides and the likeor mixtures of any of the above.

A shell can be a semiconductor material having a composition that is thesame as or different from the composition of the core. The shell cancomprise an overcoat including one or more semiconductor materials on asurface of the core. Examples of semiconductor materials that can beincluded in a shell include, but are not limited to, a Group IV element,a Group II-VI compound, a Group II-V compound, a Group III-VI compound,a Group III-V compound, a Group IV-VI compound, a Group compound, aGroup II-IV-VI compound, a Group II-IV-V compound, alloys including anyof the foregoing, and/or mixtures including any of the foregoing,including ternary and quaternary mixtures or alloys. Examples include,but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS,MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP,InSb, AlAs, AN, AlP, AlSb, TlN, TlP, TlAs, TlSb, PbO, PbS, PbSe, PbTe,Ge, Si, an alloy including any of the foregoing, and/or a mixtureincluding any of the foregoing. For example, ZnS, ZnSe or CdSovercoatings can be grown on CdSe or CdTe semiconductor nanocrystals.

In a core/shell quantum dot, the shell or overcoating may comprise oneor more layers. The overcoating can comprise at least one semiconductormaterial which is the same as or different from the composition of thecore. Preferably, the overcoating has a thickness from about one toabout ten monolayers. An overcoating can also have a thickness greaterthan ten monolayers. In certain embodiments, more than one overcoatingcan be included on a core. An example of an overcoating process isdescribed, for example, in U.S. Pat. No. 6,322,901. By adjusting thetemperature of the reaction mixture during overcoating and monitoringthe absorption spectrum of the core, overcoated materials having highemission quantum efficiencies and narrow size distributions can beobtained. A particularly exemplary coating or layer or shell, such asfor a core quantum dot, includes a Group II-VI semiconductor material.An example of a Group II-VI semiconductor material is zinc chalcogenide.One example of a Group II-VI zinc chalcogenide semiconductor materialincludes ZnS. Another example of a Group II-VI zinc chalcogenidesemiconductor material includes ZnSe. One or more additional coatings orlayers or shells can also be included in a core-shell quantum dotparticle. An additional particularly exemplary coating includesCd_(X)Zn_(1-X)S and further as a second coating over a first ZnS or ZnSecoating on a core quantum dot particle. In certain embodiments, the coreparticle can comprise a Group II-VI semiconductor material. In certainembodiments, the core particle can comprise a Group III-V semiconductormaterial. Core particles comprising other semiconductor materials canalso be used.

In certain embodiments, the quantum dot particle includes a core and afirst shell comprising zinc chalcogenide and at least a second shellcomprising a second semiconductor material.

In certain embodiments, the first shell comprises a first semiconductormaterial and has a thickness greater than or equal to the thickness of 1monolayer of the first semiconductor material.

In certain embodiments, the first shell has a thickness up to thethickness of about 20 monolayers of the first semiconductor material,for example, 1-20, 1-15, 5-20, 5-15, 8-20, and 8-15 monolayers. Otherthicknesses within or outside these ranges may also be determined to bedesirable.

In certain embodiments, the quantum dot can include a second shell. Incertain of such embodiments, the second shell can comprise a secondsemiconductor material.

In certain embodiments wherein the quantum dot includes a second shell,the second shell can have a thickness greater than or equal to thethickness of 1 monolayer of the material from which it is constituted,e.g., the second semiconductor material. In certain of such embodiments,the second shell can have a thickness up to the thickness of about 25monolayers, for example, 1-25, 1-22, 5-25, 5-22, 5-20, 8-25, 8-22, and8-18. Other thicknesses within or outside these ranges may also bedetermined to be desirable.

In certain embodiments, a quantum dot particle may include one or moreadditional shells over the second shell.

In certain embodiments, the second shell and/or additional outer shellcomprises a semiconductor material including one or more metals whereinthe one or metals comprises from 0 up to 100% cadmium.

In certain embodiments, the second shell is the outer shell of thecore-shell quantum dot particle.

In one example of a preferred embodiment, the quantum dot includes acore comprising CdSe, a first shell comprising zinc chalcogenide at athickness of about 8-15 monolayers, and a second shell comprisesCd_(1-x)Zn_(x)S wherein 0<x<1 at a thickness of about 8-18 monolayers ofCd_(1-x)Zn_(x)S.

In certain preferred embodiments, the cadmium content of a shellcomprising a semiconductor material represented by the formulaCd_(1-x)Zn_(x)S is from zero up to 100 mol % of the total Cd and Zncontent. For example, the cadmium content can be 100 mole % (Zn contentis zero), the cadmium content can be from zero up to 80 mol percent,from zero up to about 60 mol percent, from zero up to about 40 molpercent, from zero up to about 33 mol percent, from zero up to about 20mol percent, from zero up to about 15 mol percent, from zero up to about10 mol percent. In certain embodiments, the cadmium content is greaterthan zero.

In certain embodiments of the various aspects of the invention describedherein, the quantum dot can include a core comprising a firstsemiconductor material, a first shell comprising zinc chalcogenide, anda second shell comprising a second semiconductor material, wherein thefirst shell has a bandgap which is greater than that of the secondshell.

In certain embodiments of the various aspects of the invention describedherein, the quantum dot can include a core comprising a firstsemiconductor material, a first shell comprising zinc chalcogenide, anda second shell comprising a second semiconductor material, wherein thefirst shell has a bandgap which is greater than that of the secondshell, and the bandgap of the first shell is also greater than that ofthe core.

In certain embodiments of the various aspects of the invention describedherein, the quantum dot can include a core comprising a firstsemiconductor material, a first shell comprising zinc chalcogenide, asecond shell comprising a second semiconductor material, and a thirdshell comprising a third semiconductor material, wherein the third shellhas a bandgap that is the same as or greater than that of the firstshell and the second shell has a bandgap that is less than that of thefirst shell.

Such coatings are exemplary to produce a core-shell quantum dot particlein the absence of amines. Such coatings are advantageous to produce acore-shell quantum dot particle using high temperature coating methodssuch as methods which use a temperature of about 300° C. and above.

In certain embodiments, the surrounding “shell” material can have a bandgap greater than the band gap of the core material. In certain otherembodiments, the surrounding shell material can have a band gap lessthan the band gap of the core material.

In certain embodiments, the shell can be chosen so as to have an atomicspacing close to that of the “core” substrate. In certain otherembodiments, the shell and core materials can have the same crystalstructure.

Examples of quantum dot (e.g., semiconductor nanocrystal)(core)shell1/shell2 materials include, without limitation: red (e.g.,(CdSe)ZnS/CdZnS, or (CdSe)ZnSe/CdZnS (core)shell1/shell2), green (e.g.,(CdZnSe)ZnS/CdZnS, (CdSe)ZnS/ZnS, (CdSe)ZnS/CdZnS, or (CdSe)ZnSe/CdZnS(core)shell1/shell2, etc.), and blue (e.g., (CdS)ZnS/CdZnS,(CdSe)ZnS/ZnS, or (CdSe)ZnSe/ZnS (core)shell1/shell2.)

Quantum dots can have various shapes, including, but not limited to,sphere a rod, disk, other shapes, and mixtures of various shapedparticles.

Methods of making quantum dots are known. One example of a method ofmaking a quantum dot (including, for example, but not limited to, asemiconductor nanocrystal) is a colloidal growth process. Colloidalgrowth occurs by injecting an M donor and an X donor into a hotcoordinating solvent. One example of a preferred method for preparingmonodisperse quantum dots comprises pyrolysis of organometallicreagents, such as dimethyl cadmium, injected into a hot, coordinatingsolvent. This permits discrete nucleation and results in the controlledgrowth of macroscopic quantities of quantum dots. The injection producesa nucleus that can be grown in a controlled manner to form a quantumdot. The reaction mixture can be gently heated to grow and anneal thequantum dot. Both the average size and the size distribution of thequantum dots in a sample are dependent on the growth temperature. Thegrowth temperature for maintaining steady growth increases withincreasing average crystal size. Resulting quantum dots are members of apopulation of quantum dots. As a result of the discrete nucleation andcontrolled growth, the population of quantum dots that can be obtainedhas a narrow, monodisperse distribution of diameters. The monodispersedistribution of diameters can also be referred to as a “size.”Preferably, a monodisperse population of particles includes a populationof particles wherein at least about 60% of the particles in thepopulation fall within a specified particle size range. A population ofmonodisperse particles preferably deviate less than 15% rms(root-mean-square) in diameter and more preferably less than 10% rms andmost preferably less than 5%.

Another example of a method for making quantum dots comprising asemiconductor material that can be represented by the formula MX,wherein M represents one or more metals and X represents one or morechalcogens and/or one or more pnictogens, comprises combining precursorscomprising one or more M donors and one or more X donors at a reactiontemperature to form a reaction mixture. The reaction is then terminatedor quenched. In certain aspects, an X donor can be added to a solutionof a metal source or M donor at a reaction temperature to form areaction mixture. The reaction is then terminated or quenched. Incertain aspects, an M donor can be added to a solution of an X donor ata reaction temperature to form a reaction mixture. The reaction is thenterminated or quenched. In certain aspects, an M donor and an X donorcan be added to a reaction medium simultaneously. Preferably, thereaction is terminated or quenched so as to stop growth of the quantumdots before the quantum dots ripen or broaden or combine together. Thereaction can be terminated or quenched, for example, by cooling thereaction mixture to a quenching temperature effective to terminate orquench the nucleation process in a manner to stop or limit furthergrowth of the semiconductor nanocrystals. Preferably, the reactionmixture is cooled to a temperature effective to quench or stop growth ofthe semiconductor nanocrystals formed in the reaction mixture prior toripening or broadening or combining of the quantum dots. Quantum dotsare present in the reaction vessel and may be isolated or recovered. Thequantum dots in the reaction vessel or the quantum dots after isolationor recovery may be subjected to further growth by exposure to an M donorand an X donor. According to this aspect, the quantum dots are exposedto an M donor and an X donor under suitable reaction conditions suchthat the quantum dots grow in size using the M donor and X donor. The Mdonor and the X donor can be provided to a reaction vessel including thequantum dots as a substantially steady or substantially constantinfusion or feed or source such that as the M donor and the X donor areconsumed or otherwise used to grow the quantum dots, additional supplyof M donor and X donor are provided to the reaction vessel, such as in asubstantially continuous manner, to continue growth of the quantum dotsuntil a desired quantum dot size is reached.

According to certain methods of making quantum dots, the liquid mediumincludes solvents such as coordinating solvents. A coordinating solventcan help control the growth of the quantum dot. Alternatively,non-coordinating solvents can also be used in certain applications. Acoordinating solvent is a compound having a donor lone pair, forexample, a lone electron pair available to coordinate to a surface ofthe growing quantum dot (including, e.g., a semiconductor nanocrystal).Solvent coordination can stabilize the growing quantum dot. Examples ofcoordinating solvents include alkyl phosphines, alkyl phosphine oxides,alkyl phosphonic acids, or alkyl phosphinic acids, however, othercoordinating solvents, such as pyridines, furans, and amines may also besuitable for the quantum dot (e.g., semiconductor nanocrystal)production. Additional examples of suitable coordinating solventsinclude pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphineoxide (TOPO) and trishydroxylpropylphosphine (tHPP), tributylphosphine,tri(dodecyl)phosphine, dibutyl-phosphite, tributyl phosphite,trioctadecyl phosphite, trilauryl phosphite, tris(tridecyl)phosphite,triisodecyl phosphite, bis(2-ethylhexyl)phosphate,tris(tridecyl)phosphate, hexadecylamine, oleylamine, octadecylamine,bis(2-ethylhexyl)amine, octylamine, dioctylamine, trioctylamine,dodecylamine/laurylamine, didodecylamine tridodecylamine,hexadecylamine, dioctadecylamine, trioctadecylamine, phenylphosphonicacid, hexylphosphonic acid, tetradecylphosphonic acid, octylphosphonicacid, octadecylphosphonic acid, propylenediphosphonic acid,phenylphosphonic acid, aminohexylphosphonic acid, dioctyl ether,diphenyl ether, methyl myristate, octyl octanoate, N-dodecylpyrrolidone(NDP) and hexyl octanoate. In certain embodiments, technical grade TOPOcan be used. As will be appreciated by the skilled artisan, in aspectsof the invention calling for the absence or substantial absence of aminespecies, use of amine-containing solvents are preferably avoided.

According to certain aspects, reaction conditions in a process formaking quantum dots are provided where amine based components in thereaction mixture are substantially completely reacted or otherwise usedduring the process such that free or unreacted or unbound amine speciesor byproducts thereof are absent or substantially absent in the reactionmixture when quantum dots of desired size are obtained.

According to certain aspects, reaction conditions in a process formaking quantum dots are provided where amine based components in thereaction mixture are absent such that free or unreacted or unbound aminespecies or byproducts thereof are absent or substantially absent in thereaction mixture when quantum dots of desired size are obtained.

When making quantum dots using amine species resulting in bound aminespecies, such bound amine species may be removed and/or diluted awaysuch as by using a metal carboxylate species during a high temperaturecoating process resulting in quantum dots which lack or substantiallylack amine species on their surface as bound ligands. Such quantum dotsmay include core quantum dots comprising an II-VI semiconductor materialcharacterized as yellow, orange or red emitters which may be larger insize than quantum dots characterized as green or blue emitters oremitters having an emission of less than 530 nm. According to certainaspects, low energy emitters such as yellow, orange or red quantum dotsare made by growing II-VI core quantum dots and substantially completelyconsuming amine species in the reaction mixture. Once such cores areprecipitated out of solution, there are substantially no amine speciesor byproducts thereof remaining in the reaction solution and accordinglyin the core quantum dots prior to the coating process.

The narrow size distribution of the quantum dots (including, e.g.,semiconductor nanocrystals) allows the possibility of light emission innarrow spectral widths. Monodisperse semiconductor nanocrystals havebeen described in detail in Murray et al. (J. Am. Chem. Soc., 115:8706(1993)); in the thesis of Christopher Murray, entitled “Synthesis andCharacterization of II-VI Quantum Dots and Their Assembly into 3-DQuantum Dot Superlattices”, Massachusetts Institute of Technology,September, 1995. The foregoing are hereby incorporated herein byreference in their entireties.

The process of controlled growth and annealing of the quantum dots inthe coordinating solvent that follows nucleation can also result inuniform surface derivatization and regular core structures. As the sizedistribution sharpens, the temperature can be raised to maintain steadygrowth. By adding more M donor or X donor, the growth period can beshortened. Size distribution during the growth stage of the reaction canbe estimated by monitoring the absorption or emission line widths of theparticles. Modification of the reaction temperature in response tochanges in the absorption spectrum of the particles allows themaintenance of a sharp particle size distribution during growth.Reactants can be added to the nucleation solution during crystal growthto grow larger crystals. For example, for CdSe and CdTe, by stoppinggrowth at a particular semiconductor nanocrystal average diameter andchoosing the proper composition of the semiconducting material, theemission spectra of the semiconductor nanocrystals can be tunedcontinuously over the wavelength range of 300 nm to 5 microns, or from400 nm to 800 nm.

Size distribution during the growth stage of the reaction can beestimated by monitoring the absorption or emission line widths of theparticles. Modification of the reaction temperature in response tochanges in the absorption spectrum of the particles allows themaintenance of a sharp particle size distribution during growth.Reactants can be added to the nucleation solution during crystal growthto grow larger crystals. For example, for CdSe and CdTe, by stoppinggrowth at a particular semiconductor nanocrystal average diameter andchoosing the proper composition of the semiconducting material, theemission spectra of the semiconductor nanocrystals can be tunedcontinuously over the wavelength range of 300 nm to 5 microns, or from400 nm to 800 nm.

The particle size distribution of the quantum dots (including, e.g.,semiconductor nanocrystals) can be further refined by size selectiveprecipitation with a poor solvent for the quantum dots, such asmethanol/butanol. For example, quantum dots can be dispersed in asolution of 10% butanol in hexane. Methanol can be added dropwise tothis stirring solution until opalescence persists. Separation ofsupernatant and flocculate by centrifugation produces a precipitateenriched with the largest crystallites in the sample. This procedure canbe repeated until no further sharpening of the optical absorptionspectrum is noted. Size-selective precipitation can be carried out in avariety of solvent/nonsolvent pairs, including pyridine/hexane andchloroform/methanol. The size-selected quantum dot (e.g., semiconductornanocrystal) population preferably has no more than a 15% rms deviationfrom mean diameter, more preferably 10% rms deviation or less, and mostpreferably 5% rms deviation or less.

Quantum dots (e.g., semiconductor nanocrystals) preferably furtherinclude ligands attached thereto. According to one aspect, quantum dotswithin the scope of the present invention include green CdSe quantumdots having oleic acid ligands and red CdSe quantum dots having oleicacid ligands. Alternatively, or in addition, octadecylphosphonic acid(“ODPA”) ligands may be used instead of oleic acid ligands. The ligandspromote solubility of the quantum dots in the polymerizable compositionwhich allows higher loadings without agglomeration which can lead to redshifting.

Ligands can be derived from a coordinating solvent that may be includedin the reaction mixture during the growth process. Ligands can be addedto the reaction mixture. Ligands can be derived from a reagent orprecursor included in the reaction mixture for synthesizing the quantumdots. Ligands can be exchanged with ligands on the surface of a quantumdot. In certain embodiments, quantum dots can include more than one typeof ligand attached to an outer surface.

According to one aspect of the present invention, quantum dots describedherein include aliphatic ligands attached thereto. Such aliphaticligands promote adhesion with a carrier particle. Such aliphatic ligandspromote solubility or dispersability of the quantum dots bound to thecarrier particles in a curable or polymerizable matrix material.According to one aspect, exemplary ligands include fatty acid ligands,long chain fatty acid ligands, oleic acid ligands andoctadecylphosphonic acid (“ODPA”) ligands.

Ligands can be derived from a coordinating solvent that may be includedin the reaction mixture during the growth process. Alternatively,ligands can be added to the reaction mixture or ligands can be derivedfrom a reagent or precursor included in the reaction mixture forsynthesizing the quantum dots. In certain embodiments, quantum dots caninclude more than one type of ligand attached to an outer surface.

A quantum dot surface includes ligands derived from the growth processor otherwise can be modified by repeated exposure to an excess of acompeting ligand group (including, e.g., but not limited to, acoordinating group) to form an overlayer. For example, a dispersion ofthe capped quantum dots can be treated with a coordinating organiccompound, such as pyridine, to produce crystallites which dispersereadily in pyridine, methanol, and aromatics but no longer disperse inaliphatic solvents. Such a surface exchange process can be carried outwith any compound capable of coordinating to or bonding with the outersurface of the quantum dot, including, for example, but not limited to,phosphines, thiols, amines and phosphates.

For example, a quantum dot can be exposed to short chain polymers whichexhibit an affinity for the surface and which terminate in a moietyhaving an affinity for a suspension or dispersion medium. Such affinityimproves the stability of the suspension and discourages flocculation ofthe quantum dot. Examples of additional typical ligands include fattyacids, long chain fatty acids, oleic acid, alkyl phosphines, alkylphosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids,pyridines, furans, and amines. More specific examples include, but arenot limited to, pyridine, tri-n-octyl phosphine (TOP), tri-n-octylphosphine oxide (TOPO), tris-hydroxylpropylphosphine (tHPP) andoctadecylphosphonic acid (“ODPA”). Technical grade TOPO can be used. Aswill be appreciated by the skilled artisan, in aspects of the inventioncalling for the absence or substantial absence of amine species, use ofamine-containing species as ligands are preferably avoided.

Suitable coordinating ligands can be purchased commercially or preparedby ordinary synthetic organic techniques, for example, as described inJ. March, Advanced Organic Chemistry, which is incorporated herein byreference in its entirety.

According to an additional aspect, the surface of core quantum dots canbe altered or supplemented or otherwise reconstructed using metalcarboxylate species. This is particularly advantageous to remove aminespecies which may be bound to the core quantum dot. According to thisaspect, CdSe, ZnS or ZnSe may be grown on core quantum dots usingcarboxylate based precursors including Cd(Oleate)₂ and the like and thencoated with Cd_(X)Zn_(1-X)S (wherein 0<x<1) in situ. Alternatively, thequantum dots may be isolated and then coated with Cd_(X)Zn_(1-X)S usingthe high temperature coating methods described herein.

According to a certain aspect, the use of carboxylate based precursorswith small CdSe core quantum dots (less than 500 nm absorbance peak) tofurther grow the size of the quantum dots results in the surface of thequantum dots having a plurality of carboxylic acid ligands. According tothis aspect, the Cd precursor may be carboxylate based includingCd(Oleate)₂ and the Se precursor may be dialkylphosphine-selenide suchas diisobutylphosphine selenide or diphenylphosphine selenide. Thegrowth process produces high quality monodisperse CdSe cores with afirst absorbance peak tunable between 450-600 nm. The growth processallows in-situ high temperature overcoating of a first shell comprisinga zinc chalcogenide. Further formation of a second shell comprisingCd_(X)Zn_(1-X)S (wherein 0<x<1) can produce green emitters emittingbetween 500-540 nm, yellow emitters emitting between 540-590 nm and redemitters emitting between 590-630 nm with high solution quantum yield(QY) (about 80%), narrow FWHM (20-35 nm) and high external quantumefficiency in the solid state (90-95%).

According to an additional aspect, a method of making quantum dotshaving a coating thereon is provided which includes providing a reactionmixture of core quantum dots, a zinc carboxylate and a chalcogen (e.g.,sulfur, selenium, etc.) source at a temperature of greater than 280° C.in the substantial absence of an amine species and for a period of timeto complete a shell or layer or coating, such as, for example, 10minutes, 15 minutes, 30 minutes, or such other time as may be determinedby the skilled artisan; providing a first coating on the core quantumdots from the zinc carboxylate and chalcogen source to form first coatedquantum dots; combining an additional metal carboxylate and anadditional chalcogenide source with the first coated quantum dots at atemperature of greater than 280° C. in the substantial absence of anamine species; and providing a second coating on the first coatedquantum dots from the additional metal carboxylate and the additionalchalcogenide source.

According to one aspect, the core quantum dots include group II-VIelements. According to one aspect, a first coating of Zn-chalcogenide isprovided on the core quantum dots in the absence of amine species.According to one aspect, a second coating of Cd_(X)Zn_(1-X)S (wherein0<x<1) is provided on the core quantum dots in the absence of aminespecies. According to one aspect, the core quantum dots are CdSe quantumdots. According to one aspect, a reaction mixture is provided for use incoating quantum dots comprising core quantum dots, zinc carboxylate anda chalcogen source in the substantial absence of an amine species.According to one aspect, quantum dots are provided having one or morecoatings wherein the one or more coatings are substantially free ofamine species. According to one aspect, a method of making quantum dotshaving a coating thereon is provided comprising coating core quantumdots with at least one semiconductor shell in the substantial absence ofan amine species. According to one aspect, a first semiconductor shellof Zn-chalcogenide is placed on the core quantum dot. According to oneaspect, a second semiconductor shell of Cd_(X)Zn_(1-X)S (wherein 0<x<1)is placed on the first semiconductor shell of Zn-chalcogenide. Accordingto one aspect, a quantum dot is provided including a core quantum dotand at least one semiconductor shell wherein the quantum dot issubstantially free of an amine species. According to one aspect, thecore quantum dots have a first semiconductor shell of Zn-chalcogenide.According to one aspect, the core quantum dots have a secondsemiconductor shell of Cd_(X)Zn_(1-X)S (wherein 0<x<1) over the firstsemiconductor shell of Zn-chalcogenide.

According to an additional aspect, a method of making quantum dotshaving a coating thereon is provided which includes providing a reactionmixture of core quantum dots, a zinc carboxylate and a sulfur source ata temperature of greater than 240° C. in the substantial absence of anamine species and forming a first coating on the core quantum dots fromthe zinc carboxylate and sulfur source to form first coated quantumdots; combining an additional metal carboxylate and an additionalchalcogenide source with the first coated quantum dots at a temperatureof greater than 280° C. in the substantial absence of an amine species;and providing a second coating on the first coated quantum dots from theadditional metal carboxylate and the additional chalcogenide source.According to one aspect, the core quantum dots include group II-VIelements. According to one aspect, a first coating of ZnS is provided onthe core quantum dots in the absence of amine species. According to oneaspect, a second coating of Cd_(X)Zn_(1-X)S (wherein 0<x<1) is providedon the core quantum dots in the absence of amine species. According toone aspect, the core quantum dots are CdSe quantum dots. According toone aspect, a reaction mixture is provided for use in coating quantumdots comprising core quantum dots, zinc carboxylate and a sulfur sourcein the substantial absence of an amine species. According to one aspect,quantum dots are provided having one or more coatings wherein the one ormore coatings are substantially free of amine species. According to oneaspect, a method of making quantum dots having a coating thereon isprovided comprising coating core quantum dots with at least onesemiconductor shell in the substantial absence of an amine species.According to one aspect, a first semiconductor shell of ZnS is placed onthe core quantum dot. According to one aspect, a second semiconductorshell of Cd_(X)Zn_(1-X)S (wherein 0<x<1) is placed on the firstsemiconductor shell of ZnS. According to one aspect, a quantum dot isprovided including a core quantum dot and at least one semiconductorshell wherein the quantum dot is substantially free of an amine species.According to one aspect, the core quantum dots have a firstsemiconductor shell of ZnS. According to one aspect, the core quantumdots have a second semiconductor shell of Cd_(X)Zn_(1-X)S (wherein0<x<1) over the first semiconductor shell of ZnS.

In certain aspects, the first coating is formed on the core quantum dotsfrom the zinc carboxylate and sulfur source at a temperature greaterthan 240° C. (e.g., but not limited to, at least 270° C., at least 280°C., at least 290° C., at least 300° C., at least 310° C., or such othertemperature as may be determined by the skilled artisan) for a period oftime to form or complete a shell or layer or coating and/or to achieve adesired amount of alloying, such as, for example, 1 minute, 2 minutes, 5minutes, 10 minutes, 15 minutes, 30 minutes, or such other time as maybe determined by the skilled artisan.

According to an additional aspect, a method of making quantum dotshaving a coating thereon is provided which includes providing a reactionmixture of core quantum dots, a zinc carboxylate and a selenium sourceat a temperature of greater than 300° C. in the substantial absence ofan amine species and for a period of time to complete a shell or layeror coating, such as, for example, 10 minutes, 15 minutes, 30 minutes, orsuch other time as may be determined by the skilled artisan; providing afirst coating on the core quantum dots from the zinc carboxylate andselenium source to form first coated quantum dots; combining anadditional metal carboxylate and an additional chalcogenide source withthe first coated quantum dots at a temperature of greater than 280° C.in the substantial absence of an amine species; and providing a secondcoating on the first coated quantum dots from the additional metalcarboxylate and the additional chalcogenide source. According to oneaspect, the core quantum dots include group II-VI elements. According toone aspect, a first coating of ZnSe is provided on the core quantum dotsin the absence of amine species. According to one aspect, a secondcoating of Cd_(X)Zn_(1-X)S (wherein 0<x<1) is provided on the corequantum dots in the absence of amine species. According to one aspect,the core quantum dots are CdSe quantum dots. According to one aspect, areaction mixture is provided for use in coating quantum dots comprisingcore quantum dots, zinc carboxylate and a selenium source in thesubstantial absence of an amine species. According to one aspect,quantum dots are provided having one or more coatings wherein the one ormore coatings are substantially free of amine species. According to oneaspect, a method of making quantum dots having a coating thereon isprovided comprising coating core quantum dots with at least onesemiconductor shell in the substantial absence of an amine species.According to one aspect, a first semiconductor shell of ZnSe is placedon the core quantum dot. According to one aspect, a second semiconductorshell of Cd_(X)Zn_(1-X)S (wherein 0<x<1) is placed on the firstsemiconductor shell of ZnSe. According to one aspect, a quantum dot isprovided including a core quantum dot and at least one semiconductorshell wherein the quantum dot is substantially free of an amine species.According to one aspect, the core quantum dots have a firstsemiconductor shell of ZnSe. According to one aspect, the core quantumdots have a second semiconductor shell of Cd_(X)Zn_(1-X)S (wherein0<x<1) over the first semiconductor shell of ZnSe.

In certain embodiments, a dispersion of CdSe cores in a liquid mediumare heated up to 320° C. in the presence of a zinc carboxylate (e.g.,Zn(Oleate)₂). At 320° C., a chalcogen source is introduced over a periodof, for example, 15 minutes, as the temperature is maintained between320-330° C. The amount of Zn and chalcogen determine the thickness ofthe first shell, and Zn is preferably included in the reaction mixturein molar excess while the first shell is formed. At the end of theaddition of chalcogen, the CdSe/Zn-chalcogen core/shell material ispreferably annealed (e.g., at a temperature between 320-330° C. for5minutes), upon which secondary shell precursors are infused over apreselected period of time at a preselected temperature. In certainembodiments, the temperature can be at or about the temperature at whichthe first shell is annealed. At the end of the infusion of precursorsfor the second shell, the core/shelll/shell2 sample is preferablyannealed (e.g., at a temperature of 320-330° C.). The reaction mixturecan thereafter be cooled or otherwise returned to room temperature. Thecore/shelll/shell2 nanocrystals can thereafter be purified. In oneparticular example, the second shell precursors include Cd(Oleate)₂,Zn(Oleate)₂, and dodecanethiol. Preferably, such precursors are infusedover a period of 30 minutes at a temperature held between 320-330° C.;at the end of the precursor infusion, the core/shelll/shell2 sample canbe annealed for 5 minutes at 320-330° C., and cooled to room temperaturefor purification.

In one particular example, a first shell comprising ZnSe can be preparedas follows. The quantum dot core to be coated is put into a reactionvessel along with a zinc carboxylate precursor (e.g., Zn(Oleate)₂). Theamount of the zinc carboxylate precursor present in the reaction vesselrelative to the core can determine the number of monolayers of the firstshell that can be formed. The reaction vessel with cores and the zinccarboxylate precursor is heated up to a temperature greater than 300° C.(e.g., 320° C.), upon which a solution of selenium precursor (e.g.,diisobutylphosphine selenide (DIBP-Se) dissolved in n-dodecylpyrrolidone(NDP)) is infused. The amount of selenium precursor infused is equal to0.6 molar equivalents to the Zn in the zinc carboxylate precursorpresent in the reaction vessel, and this amount is delivered in acontrolled manner over a preselected period of time (e.g., 15 min at320-330° C.). A molar excess of Zn to Se is most preferred. For example,as the Se to Zn molar equivalent is varied from 0.6 to 1.0, a sharpdecrease in final Core/Shell EQE is observed as the ratio approaches1.0.

The thickness of the first shell comprising ZnSe can be varied from 1monolayer (also abbreviated herein as “ML”) to up to 20 ML. For example,a first shell comprising ZnSe with a thickness from 1 to 17 ML hasdemonstrated maintenance of >95% EQE. It is generally observed that thethicker the first shell comprising ZnSe, the less the EQE drops at hightemperature. For example, for first shell comprising ZnSe with athickness of about 8.5ML, the final core/shell EQE drops less than 1% upto 140° C.; from 8.5ML to 15ML <1% drop in EQE can be achieved attemperatures up to 140° C. with maintenance of an initial EQE of >95%.In certain embodiments, as the thickness of the first shell comprisingZnSe is increased, the total infusion time is preferably fixed, e.g., at15 min

In certain embodiments, an additional shell comprising Cd_(1-x)Zn_(x)S(wherein 0<x<1) can be added after a first shell comprising a zincchalcogenide. The additional shell is preferably formed after the firstshell in an in situ fashion (e.g., without isolation of the particleprior to formation of the additional shell). For example, a cadmiumprecursor (e.g., Cd(Oleate)₂) and zinc precursor (e.g., Zn(Oleate)₂) aremixed at varying proportions, from greater than 0% Cd to 100% Cd. Thesulfur precursor is preferably a long-chain aliphatic thiol, such asdodecanethiol.

In certain preferred embodiments, the ratio of the molar equivalents ofsulfur to the total molar equivalents of Cd+Zn is greater than one. Forexample, the ratio can be from greater than one to 4. It is observedthat variations in this ratio can affect the total incorporation of Znrelative to Cd into the shell, as well as the final optical properties,such as absorbance profile, EQE, and emission wavelength. As theSulfur:Metal ratio is increased from 1 to 4, the following has beenobserved:

-   -   An increase in the absorbance spectrum of the final core/shell        particle at 325 nm versus 450 nm as the sulfur ratio is        increased.    -   A decrease in solubility in a non-polar solvent such as Toluene        after purification of the resulting quantum dots as the sulfur        ratio is increased during overcoating.    -   A plateau in terms of EQE at ratios of 2-3, with a drop in EQE        as the ratio approaches 4.

Table 1 below outlines the effect of varying the sulfur to (totalcadmium+zinc) in forming a second semiconductor shell of Cd_(X)Zn_(1-X)Sover a first semiconductor shell comprising ZnSe over a core comprisingCdSe.

TABLE 1 The Effect Of Varying The Sulfur:Metal Ratio On The Optical AndSolution Properties Of The Final Core/Shell Material Emission Solubilityin Sample S:M Ratio (FWHM) % EQE Toluene 153-836 2 587 (23) 98% Good153-837 3 580 (20) 95% Good 153-831 4 577 (20) 92% Poor

The effect of varying the equivalents of Sulfur to Total equivalents ofcadmium+zinc in the second shell overcoating preparation on theabsorbance spectrum is shown in FIG. 3.

The emission from a quantum dot capable of emitting light can be anarrow Gaussian emission band that can be tuned through the completewavelength range of the ultraviolet, visible, or infra-red regions ofthe spectrum by varying the size of the quantum dot, the composition ofthe quantum dot, or both. For example, a semiconductor nanocrystalcomprising CdSe can be tuned in the visible region; a semiconductornanocrystal comprising InAs can be tuned in the infra-red region. Thenarrow size distribution of a population of quantum dots capable ofemitting light can result in emission of light in a narrow spectralrange. The population can be monodisperse preferably exhibiting lessthan a 15% rms (root-mean-square) deviation in diameter of such quantumdots, more preferably less than 10%, most preferably less than 5%.Spectral emissions in a narrow range of no greater than about 75 nm,preferably no greater than about 60 nm, more preferably no greater thanabout 40 nm, and most preferably no greater than about 30 nm full widthat half max (FWHM) for such quantum dots that emit in the visible can beobserved. IR-emitting quantum dots can have a FWHM of no greater than150 nm, or no greater than 100 nm. Expressed in terms of the energy ofthe emission, the emission can have a FWHM of no greater than 0.05 eV,or no greater than 0.03 eV. The breadth of the emission decreases as thedispersity of the light-emitting quantum dot diameters decreases.

Quantum dots can have emission quantum efficiencies such as between 0%to greater than 95%, for example in solution, such as greater than 10%,20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

The narrow FWHM of quantum dots can result in saturated color emission.The broadly tunable, saturated color emission over the entire visiblespectrum of a single material system is unmatched by any class oforganic chromophores (see, for example, Dabbousi et al., J. Phys. Chem.101, 9463 (1997), which is incorporated by reference in its entirety). Amonodisperse population of quantum dots will emit light spanning anarrow range of wavelengths.

In certain embodiments of the present invention, quantum dots that emitwavelengths characteristic of red light are desirable. In certainpreferred embodiments, quantum dots capable of emitting red light emitlight having a peak center wavelength in a range from about 615 nm toabout 635 nm, and any wavelength in between whether overlapping or not.For example, the quantum dots can be capable of emitting red lighthaving a peak center wavelength of about 630 nm, of about 625 nm, ofabout 620 nm, or of about 615 nm.

In certain embodiments of the present invention, quantum dots that emita wavelength characteristic of green light are desirable. In certainpreferred embodiments, quantum dots capable of emitting green light emitlight having a peak center wavelength in a range from about 520 nm toabout 545 nm, and any wavelength in between whether overlapping or not.For example, the quantum dots can be capable of emitting green lighthaving a peak center wavelength of about 520 nm, of about 525 nm, ofabout 535 nm, or of about 540 nm.

According to further aspects of the present invention, the quantum dotsexhibit a narrow emission profile in the range of between about 20 nmand about 60 nm at full width half maximum (FWHM). The narrow emissionprofile of quantum dots of the present invention allows the tuning ofthe quantum dots and mixtures of quantum dots to emit saturated colorsthereby increasing color gamut and power efficiency beyond that ofconventional LED lighting displays. According to one aspect, greenquantum dots designed to emit a predominant wavelength of, for example,about 523 nm and having an emission profile with a FWHM of about, forexample, 37 nm are combined, mixed or otherwise used in combination withred quantum dots designed to emit a predominant wavelength of about, forexample, 617 nm and having an emission profile with a FWHM of about, forexample 32 nm. Such combinations can be stimulated by blue light tocreate trichromatic white light.

Quantum dots in accordance with the present invention can be included invarious formulations depending upon the desired utility. According toone aspect, quantum dots are included in flowable formulations orliquids to be included, for example, into clear vessels which are to beexposed to light. Such formulations can include various amounts of oneor more type of quantum dots and one or more host materials. Suchformulations can further include one or more scatterers. Other optionaladditives or ingredients can also be included in a formulation. Incertain embodiments, a formulation can further include one or more photoinitiators. One of skill in the art will readily recognize from thepresent invention that additional ingredients can be included dependingupon the particular intended application for the quantum dots.

An optical material, other composition, or formulation within the scopeof the invention may include a host material, such as in the case of anoptical component, which may be present in an amount from about 50weight percent and about 99.5 weight percent, and any weight percent inbetween whether overlapping or not. In certain embodiment, a hostmaterial may be present in an amount from about 80 to about 99.5 weightpercent. Examples of specific useful host materials include, but are notlimited to, polymers, oligomers, monomers, resins, binders, glasses,metal oxides, and other nonpolymeric materials. Preferred host materialsinclude polymeric and non-polymeric materials that are at leastpartially transparent, and preferably fully transparent, to preselectedwavelengths of light. In certain embodiments, the preselectedwavelengths can include wavelengths of light in the visible (e.g.,400-700 nm) region of the electromagnetic spectrum. Preferred hostmaterials include cross-linked polymers and solvent-cast polymers.Examples of other preferred host materials include, but are not limitedto, glass or a transparent resin. In particular, a resin such as anon-curable resin, heat-curable resin, or photocurable resin is suitablyused from the viewpoint of processability. Specific examples of such aresin, in the form of either an oligomer or a polymer, include, but arenot limited to, a melamine resin, a phenol resin, an alkyl resin, anepoxy resin, a polyurethane resin, a maleic resin, a polyamide resin,polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol,polyvinylpyrrolidone, hydroxyethylcellulose, carboxymethylcellulose,copolymers containing monomers or oligomers forming these resins, andthe like. Other suitable host materials can be identified by persons ofordinary skill in the relevant art.

Host materials can also comprise silicone materials. Suitable hostmaterials comprising silicone materials can be identified by persons ofordinary skill in the relevant art.

In certain embodiments and aspects of the inventions contemplated bythis invention, a host material comprises a photocurable resin. Aphotocurable resin may be a preferred host material in certainembodiments, e.g., in embodiments in which the composition is to bepatterned. As a photo-curable resin, a photo-polymerizable resin such asan acrylic acid or methacrylic acid based resin containing a reactivevinyl group, a photo-crosslinkable resin which generally contains aphoto-sensitizer, such as polyvinyl cinnamate, benzophenone, or the likemay be used. A heat-curable resin may be used when the photo-sensitizeris not used. These resins may be used individually or in combination oftwo or more.

In certain embodiments and aspects of the inventions contemplated bythis invention, a host material can comprise a solvent-cast resin. Apolymer such as a polyurethane resin, a maleic resin, a polyamide resin,polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol,polyvinylpyrrolidone, hydroxyethylcellulose, carboxymethylcellulose,copolymers containing monomers or oligomers forming these resins, andthe like can be dissolved in solvents known to those skilled in the art.Upon evaporation of the solvent, the resin forms a solid host materialfor the semiconductor nanoparticles.

In certain embodiments, acrylate monomers and/or acrylate oligomerswhich are commercially available from Radcure and Sartomer can bepreferred.

Quantum dots can be encapsulated. Nonlimiting examples of encapsulationmaterials, related methods, and other information that may be useful aredescribed in International Application No. PCT/US2009/01372 of Linton,filed 4 Mar. 2009 entitled “Particles Including Nanoparticles, UsesThereof, And Methods” and U.S. Patent Application No. 61/240932 of Nicket al., filed 9 Sep. 2009 entitled “Particles Including Nanoparticles,Uses Thereof, And Methods”, each of the foregoing being herebyincorporated herein by reference in its entirety.

The total amount of quantum dots included in an optical material, suchas a host material for example a polymer matrix, within the scope of theinvention is preferably in a range from about 0.05 weight percent toabout 5 weight percent, and any weight percent in between whetheroverlapping or not. The amount of quantum dots included in an opticalmaterial can vary within such range depending upon the application andthe form in which the quantum dots are included (e.g., film, optics(e.g., capillary), encapsulated film, etc.), which can be chosen basedon the particular end application. For instance, when an optic materialis used in a thicker capillary with a longer pathlength (e.g., such asin a backlight unit (BLU) for large screen television applications), theconcentration of quantum dots can be closer to 0.5%. When an opticalmaterial is used in a thinner capillary with a shorter pathlength (e.g.,such as in BLUs for mobile or hand-held applications), the concentrationof quantum dots can be closer to 5%.

The quantum dots used in a formulation, optical material, or othercomposition are selected based on the desired peak emission wavelengthor combinations of wavelengths described for the particular intendend-use application for the formulation, optical material, or othercomposition.

When quantum dots emit light with peak emission wavelengths that differfrom that of other quantum dots included in a particular embodiments,the amounts of each are selected based on the desired light out-put.Such determination can be readily made by the person of ordinary skillin the relevant art. For example, the ratio of quantum dots withdifferent peak emissions that are used in an optical material isdetermined by the emission peaks of the quantum dots used. For example,when quantum dots capable of emitting green light having a peak centerwavelength in a range from about 514 nm to about 545 nm, and anywavelength in between whether overlapping or not, and quantum dotscapable of emitting red light having a peak center wavelength in a rangefrom about 615 nm to about 645 nm, and any wavelength in between whetheroverlapping or not, are used in an optical material, the ratio of theweight percent green-emitting quantum dots to the weight percent ofred-emitting quantum dots can be in a range from about 12:1 to about1:1, and any ratio in between whether overlapping or not.

The above ratio of weight percent green-emitting quantum dots to weightpercent red-emitting quantum dots in an optical material canalternatively be presented as a molar ratio. For example, the aboveweight percent ratio of green to red quantum dots can correspond to agreen to red quantum dot molar ratio in a range from about 24.75 to 1 toabout 5.5 to 1, and any ratio in between whether overlapping or not.

The ratio of the blue to green to red light output intensity in whitetrichromatic light emitted by a quantum dot containing BLU describedherein including blue-emitting solid state inorganic semiconductor lightemitting devices (having blue light with a peak center wavelength in arange from about 450 nm to about 460 nm, and any wavelength in betweenwhether overlapping or not), and an optical material including mixturesof green-emitting quantum dots and red-emitting quantum dots within theabove range of weight percent ratios, can vary within the range. Forexample, the ratio of blue to green light output intensity therefor canbe in a range from about 0.75 to about 4 and the ratio of green to redlight output intensity therefor can be in a range from about 0.75 toabout 2.0. In certain embodiments, for example, the ratio of blue togreen light output intensity can be in a range from about 1.4 to about2.5 and the ratio of green to red light output intensity can be in arange from about 0.9 to about 1.3.

Scatterers, also referred to as scattering agents, within the scope ofthe invention may be present, for example, in an amount of between about0.01 weight percent and about 1 weight percent. Amounts of scatterersoutside such range may also be useful. Examples of light scatterers(also referred to herein as scatterers or light scattering particles)that can be used in the embodiments and aspects of the inventionsdescribed herein, include, without limitation, metal or metal oxideparticles, air bubbles, and glass and polymeric beads (solid or hollow).Other light scatterers can be readily identified by those of ordinaryskill in the art. In certain embodiments, scatterers have a sphericalshape. Preferred examples of scattering particles include, but are notlimited to, TiO₂, SiO₂, BaTiO₃, BaSO₄, and ZnO. Particles of othermaterials that are non-reactive with the host material and that canincrease the absorption pathlength of the excitation light in the hostmaterial can be used. In certain embodiments, light scatterers may havea high index of refraction (e.g., TiO₂, BaSO₄, etc) or a low index ofrefraction (gas bubbles).

Selection of the size and size distribution of the scatterers is readilydeterminable by those of ordinary skill in the relevant art. The sizeand size distribution can be based upon the refractive index mismatch ofthe scattering particle and the host material in which the lightscatterers are to be dispersed, and the preselected wavelength(s) to bescattered according to Rayleigh scattering theory. The surface of thescattering particle may further be treated to improve dispersability andstability in the host material. In one embodiment, the scatteringparticle comprises TiO₂ (R902+ from DuPont) of 0.2 μm particle size, ina concentration in a range from about 0.01 to about 1% by weight.

The amount of scatterers in a formulation is useful in applicationswhere the formulation which may be in the form of an ink is contained ina clear vessel having edges to limit losses due the total internalreflection. The amount of the scatterers may be altered relative to theamount of quantum dots used in the formulation. For example, when theamount of the scatter is increased, the amount of quantum dots may bedecreased.

Examples of thixotropes which may be included in a quantum dotformulation, also referred to as rheology modifiers, include, but arenot limited to, fumed metal oxides (e.g., fumed silica which can besurface treated or untreated (such as Cab-O-Sil® fumed silica productsavailable from Cabot Corporation)) or fumed metal oxide gels (e.g., asilica gel). An optical material can include an amount of thixotrope ina range from about 5 to about 12 weight percent. Other amounts outsidethe range may also be determined to be useful or desirable.

In certain embodiments, a formulation including quantum dots and a hostmaterial can be formed from an ink comprising quantum dots and a liquidvehicle, wherein the liquid vehicle comprises a composition includingone or more functional groups or units that are capable of beingcross-linked. The functional units can be cross-linked, for example, byUV treatment, thermal treatment, or another cross-linking techniquereadily ascertainable by a person of ordinary skill in a relevant art.In certain embodiments, the composition including one or more functionalgroups that are capable of being cross-linked can be the liquid vehicleitself. In certain embodiments, it can be a co-solvent. In certainembodiments, it can be a component of a mixture with the liquid vehicle.

One particular example of a preferred method of making an ink is asfollows. A solution including quantum dots having the desired emissioncharacteristics well dispersed in an organic solvent is concentrated tothe consistency of a wax by first stripping off the solvent undernitrogen/vacuum until a quantum dot containing residue with the desiredconsistency is obtained. The desired resin monomer is then added undernitrogen conditions, until the desired monomer to quantum dot ratio isachieved. This mixture is then vortex mixed under oxygen free conditionsuntil the quantum dots are well dispersed. The final components of theresin are then added to the quantum dot dispersion, and are thensonicated mixed to ensure a fine dispersion.

A tube or capillary comprising an optical material prepared from suchfinished ink can be prepared by then introducing the ink into the tubevia a wide variety of methods, and then UV cured under intenseillumination for some number of seconds for a complete cure.

In certain aspects and embodiments of the inventions taught herein, theoptic including the cured quantum dot containing ink is exposed to lightflux for a period of time sufficient to increase the photoluminescentefficiency of the optical material.

In certain embodiments, the optical material is exposed to light andheat for a period of time sufficient to increase the photoluminescentefficiency of the optical material.

In preferred certain embodiments, the exposure to light or light andheat is continued for a period of time until the photoluminescentefficiency reaches a substantially constant value.

In one embodiment, for example, after the optic, i.e. tube or capillary,is filled with quantum dot containing ink, cured, and sealed (regardlessof the order in which the curing and sealing steps are conducted), theoptic is exposed, to 25-35 mW/cm² light flux with a wavelength in arange from about 365 nm to about 470 nm, while at a temperature in arange from about 25 to 80° C., for a period of time sufficient toincrease the photoluminescent efficiency of the ink. In one embodiment,for example, the light has a wavelength of about 450 nm, the light fluxis 30 mW/cm², the temperature 80° C., and the exposure time is 3 hours.

In general, quantum dots according to the present invention can have anaverage particle size in a range from about 1 to about 1000 nanometers(nm), and preferably in a range from about 1 to about 100 nm. In certainembodiments, quantum dots have an average particle size in a range fromabout 1 to about 20 nm (e.g., such as about 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, or 20 nm). In certain embodiments, quantumdots have an average particle size in a range from about 1 nm to about20 nm or about 1 nm to about 10 nm. Quantum dots can have an averagediameter less than about 150 Angstroms (A). In certain embodiments,quantum dots having an average diameter in a range from about 12 toabout 150 A can be particularly desirable. However, depending upon thecomposition, structure, and desired emission wavelength of the quantumdot, the average diameter may be outside of these ranges.

The particle size distribution of the quantum dots (including, e.g.,semiconductor nanocrystals) can be further refined by size selectiveprecipitation with a poor solvent for the quantum dots, such asmethanol/butanol. For example, quantum dots can be dispersed in asolution of 10% butanol in hexane. Methanol can be added drop wise tothis stirring solution until opalescence persists. Separation ofsupernatant and flocculate by centrifugation produces a precipitateenriched with the largest crystallites in the sample. This procedure canbe repeated until no further sharpening of the optical absorptionspectrum is noted. Size-selective precipitation can be carried out in avariety of solvent/nonsolvent pairs, including pyridine/hexane andchloroform/methanol. The size-selected quantum dot (e.g., semiconductornanocrystal) population preferably has no more than a 15% rms deviationfrom mean diameter, more preferably 10% rms deviation or less, and mostpreferably 5% rms deviation or less.

According to one aspect, a formulation or composition includes a hostmaterial that is photopolymerizable. The formulation or composition inthe form of a fluid can be placed within the tube or other container andthen one or both ends sealed with the tube being hermetically sealed toavoid oxygen being within a tube. Alternatively, the formulation orcomposition can be disposed between opposing plates and/or sheets withthe perimeter edges being hermetically sealed. Quantum dots may bepresent in the polymerizable composition in an amount from about 0.05%w/w to about 5.0% w/w. According to one aspect, the polymerizablecomposition is photopolymerizable. The polymerizable composition is inthe form of a fluid which can be placed within the tube and then one orboth ends sealed with the tube being hermetically sealed to avoid oxygenbeing within the tube. The polymerizable composition is then subjectedto light of sufficient intensity and for a period of time sufficient topolymerize the polymerizable composition, and in one aspect, in theabsence of oxygen. In certain embodiments, the period of time can rangebetween about 10 seconds to about 6 minutes or between about 1 minute toabout 6 minutes. According to one embodiment, the period of time issufficiently short to avoid agglomeration of the quantum dots prior toformation of a polymerized matrix. Agglomeration can result in FRET andsubsequent loss of photoluminescent performance.

A host material can include a combination of one or more polymerizablehost materials. A polymer or matrix in which quantum dots are dispersedis an example of a host material. Host materials include polymeric andnon-polymeric materials that are at least partially transparent, andpreferably fully transparent, to preselected wavelengths of light.

According to an additional aspect, a polymerizable host material isselected so as to provide sufficient ductility to the polymerizedmatrix. Ductility can be advantageous in relieving stress on thin walledglass tubes that can occur during polymer shrinkage when the polymermatrix is cured. Suitable polymerizable materials can act as solventsfor the quantum dots and so combinations of polymerizable host materialscan be selected based on solvent properties for various quantum dots.

Polymerizable host materials include monomers and oligomers and polymersand mixtures thereof. Exemplary monomers include lauryl methacrylate,norbornyl methacrylate, Ebecyl 150 (Cytec), CD590 (Cytec) and the like.Polymerizable materials can be present in the polymerizable formulationin an amount greater than 50 weight percent. Examples include amounts ina range greater than 50 to about 99.5 weight percent, greater than 50 toabout 98 weight percent, greater than 50 to about 95 weight percent,from about 80 to about 99.5 weight percent, from about 90 to about 99.95weight percent, from about 95 to about 99.95 weight percent. Otheramounts outside these examples may also be determined to be useful ordesirable.

Exemplary polymerizable compositions further include one or more of acrosslinking agent, a scattering agent, a rheology modifier, a filler,and a photoinitiator.

Suitable crosslinking agents include ethylene glycol dimethacrylateEbecyl 150 and the like. Crosslinking agents can be present in thepolymerizable formulation in an amount between about 0.5 wt % and about3.0 wt %. Crosslinking agents are generally added, for example in anamount of 1% w/w, to improve stability and strength of a polymer matrixwhich helps avoid cracking of the matrix due to shrinkage upon curing ofthe matrix.

Suitable scattering agents include TiO₂, alumina, barium sulfate, PTFE,barium titanate and the like. Scattering agents can be present in thepolymerizable formulation in an amount between about 0.05 wt % and about1.0 wt %. Scattering agents are generally added, for example in apreferred amount of about 0.15% w/w, to promote outcoupling of emittedlight.

Suitable rheology modifiers (thixotropes) include fumed silicacommercially available from Cabot Corporation such as TS-720 treatedfumed silica, treated silica commercially available from CabotCorporation such as TS720, TS500, TS530, TS610 and hydrophilic silicasuch as M5 and EHS commercially available from Cabot Corporation.Rheology modifiers can be present in the polymerizable formulation in anamount between about 5% w/w to about 12% w/w. Rheology modifiers orthixotropes act to lower the shrinkage of the matrix resin and helpprevent cracking. Hydrophobic rheology modifiers disperse more easilyand build viscosity at higher loadings allowing for more filler contentand less shrinkage to the point where the formulation becomes tooviscous to fill the tube. Rheology modifiers such as fumed silica alsoprovide higher EQE and help to prevent settling of TiO₂ on the surfaceof the tube before polymerization has taken place.

Suitable fillers include silica, fumed silica, precipitated silica,glass beads, PMMA beads and the like. Fillers can be present in thepolymerizable formulation in an amount between about 0.01% and about60%, about 0.01% and about 50%, about 0.01% and about 40%, about 0.01%and about 30%, about 0.01% and about 20% and any value or range inbetween whether overlapping or not.

Suitable photoinitiators include Irgacure 2022, KTO-46 (Lambert),Esacure 1 (Lambert) and the like. Photoinitiators can be present in thepolymerizable formulation in an amount between about 1% w/w to about 5%w/w. Photoinitiators generally help to sensitize the polymerizablecomposition to UV light for photopolymerization.

Additional information that may be useful in connection with the presentinvention and the inventions described herein is included inInternational Application No. PCT/US2009/002796 of Coe-Sullivan et al,filed 6 May 2009, entitled “Optical Components, Systems Including AnOptical Component, And Devices”; International Application No.PCT/US2009/002789 of Coe-Sullivan et al, filed 6 May 2009, entitled“Solid State Lighting Devices Including Quantum Confined SemiconductorNanoparticles, An Optical Component For A Solid State Light Device, AndMethods”; International Application No. PCT/US2010/32859 of Modi et al,filed 28 Apr. 2010 entitled “Optical Materials, Optical Components, AndMethods”; International Application No. PCT/US2010/032799 of Modi et al,filed 28 Apr. 2010 entitled “Optical Materials, Optical Components,Devices, And Methods”; International Application No. PCT/US2011/047284of Sadasivan et al, filed 10 Aug. 2011 entitled “Quantum Dot BasedLighting”; International Application No. PCT/US2008/007901 of Linton etal, filed 25 Jun. 2008 entitled “Compositions And Methods IncludingDepositing Nanomaterial”; U.S. Patent Application No. 12/283609 ofCoe-Sullivan et al, filed 12 Sep. 2008 entitled “Compositions, OpticalComponent, System Including An Optical Component, Devices, And OtherProducts”; each of the foregoing being hereby incorporated herein byreference in its entirety.

In accordance with a still further aspect of the present invention,there is provided a composition including at least one quantum dotdescribed herein. In certain embodiments of the composition, the solidstate photoluminescence efficiency of the composition is at least 80% ata temperature of 90° C. or above. In certain embodiments of thecomposition, the solid state photoluminescence efficiency of thecomposition at a temperature of 90° C. or above is at least 95% of thesolid state photoluminescence efficiency of the composition at 25° C. Incertain embodiments, the composition further includes a host material.

In accordance with a still further aspect of the present invention,there is provided an optical material comprising at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided a light emitting material comprising at least onequantum dot described herein.

In accordance with a still further aspect of the present invention,there is provided an optical component including at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided a backlighting unit including at least one quantum dotdescribed herein.

In accordance with a still further aspect of the present invention,there is provided a display including at least one quantum dot describedherein.

In accordance with a still further aspect of the present invention,there is provided an electronic device including at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided an opto-electronic device including at least onequantum dot described herein.

In accordance with a still further aspect of the present invention,there is provided a light-emitting device including at least one quantumdot described herein.

In accordance with a still further aspect of the present invention,there is provided a lamp including at least one quantum dot describedherein.

In accordance with a still further aspect of the present invention,there is provided a light bulb including at least one quantum dotdescribed herein.

In accordance with a still further aspect of the present invention,there is provided a luminaire including at least one quantum dotdescribed herein.

In accordance with yet another aspect of the present invention, there isprovided a population of quantum dots including at least on quantum dotdescribed herein. In certain embodiments, the light emitted by thepopulation has a peak emission at a predetermined wavelength with anFWHM less than about 60 nm. In certain embodiments, the FWHM is in arange from about 15 to about 50 nm.

In accordance with yet another aspect of the present invention, there isprovided a population of quantum dots prepared in accordance with any ofthe methods described herein. In certain embodiments, the light emittedby the population has a peak emission at a predetermined wavelength withan FWHM less than about 60 nm. In certain embodiments, the FWHM is in arange from about 15 to about 50 nm.

In accordance with a still further aspect of the present invention,there is provided a composition including at least one quantum dotprepared in accordance with any of the methods described herein. Incertain embodiments of the composition, the solid statephotoluminescence efficiency of the composition is at least 80% at atemperature of 90° C. or above. In certain embodiments of thecomposition, the solid state photoluminescence efficiency of thecomposition at a temperature of 90° C. or above is at least 95% of thesolid state photoluminescence efficiency of the composition at 25° C. Incertain embodiments, the composition further includes a host material.

In accordance with a still further aspect of the present invention,there is provided an optical material comprising at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a light emitting material comprising at least onequantum dot prepared in accordance with any of the methods describedherein.

In accordance with a still further aspect of the present invention,there is provided an optical component including at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a backlighting unit including at least one quantum dotprepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a display including at least one quantum dot preparedin accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided an electronic device including at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided an opto-electronic device including at least onequantum dot prepared in accordance with any of the methods describedherein.

In accordance with a still further aspect of the present invention,there is provided a light-emitting device including at least one quantumdot prepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a lamp including at least one quantum dot prepared inaccordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a light bulb including at least one quantum dotprepared in accordance with any of the methods described herein.

In accordance with a still further aspect of the present invention,there is provided a luminaire including at least one quantum dotprepared in accordance with any of the methods described herein.

In certain embodiments of the various aspects and embodiments of theinventions described herein, the quantum dot core and shells areundoped.

In certain embodiments of the various aspects and embodiments of theinventions described herein, a quantum dot described herein can beincluded in a device, component, or product in the form of a compositionin which it is included.

The present invention will be further clarified by the followingexamples, which are intended to be exemplary of the present invention.

EXAMPLE I Coating Core Quantum Dots Using a Coating Process WithoutAmine Species To Produce A Green Emitter

Preparation of semiconductor nanocrystals capable of emitting greenlight are prepared with oleic acid as follows in the absence of aminespecies.

Synthesis of CdSe Cores: 262.5 mmol of cadmium acetate is dissolved in3.826 mol of tri-n-octylphosphine at 100° C. in a 3 L 3-neckround-bottom flask and then dried and degassed for one hour. 4.655 molof trioctylphosphine oxide and 599.16 mmol of octadecylphosphonic acidare added to a 5 L stainless steel reactor and dried and degassed at140° C. for one hour. After degassing, the Cd solution is added to thereactor containing the oxide/acid and the mixture is heated to 310° C.under nitrogen. Once the temperature reached 310° C., the heating mantleis removed from the reactor and 731 mL of 1.5 M diisobutylphosphineselenide (DIBP-Se) (900.2 mmol Se) in 1-Dodecyl-2-pyrrolidinone (NDP) isthen rapidly injected. The reactor is then immediately submerged in apartially frozen (via liquid nitrogen) squalane bath rapidly reducingthe temperature of the reaction to below 100° C. The first absorptionpeak of the nanocrystals is 480 nm. The CdSe cores are precipitated outof the growth solution inside a nitrogen atmosphere glovebox by adding a3:1 mixture of methanol and isopropanol. The isolated cores are thendissolved in hexane and used to make core-shell materials. The isolatedmaterial specifications are as follows: Optical Density @ 350 nm=1.62;Abs=486 nm; Emission=509 nm; FWHM=38 nm; Total Volume=1.82 L of hexane.

Synthesis of CdSe/ZnS/CdZnS Core-Shell Nanocrystals: 335 mL ofoctadecene (ODE), 68 4 mmol of zinc acetate, and 38 mL of oleic acid areloaded into a 1 L glass reactor and degassed at 100° C. for 1 hour. In a1 L 3-neck flask, 100 mL of ODE is degassed at 120° C. for 1 hour. Afterdegassing, the temperature of the flask is reduced to 65° C. and then23.08 mmol of CdSe cores from the procedure above (275 mL) are blendedinto the 100 mL of degassed ODE and the hexane is removed under reducedpressure. The temperature of the reactor is then raised to 310° C. In aglove box, the core/ODE solution and 40 mL of octanethiol are added to a180 or 360 mL container. In a 600 mL container, 151 mL of 0.5 MZn(Oleate)₂ in TOP, 37 mL of 1.0 M Cd(Oleate)₂ in TOP, and 97 mL of 2 MTOP-S are added. Once the temperature of the reactor hit 310° C., theODE/QD cores/Octanethiol mixture is injected into the reactor andallowed to react for 30 min at 300° C. After this reaction period, theZn(Oleate)₂/Cd(Oleate)₂/TOP-S mixture is injected to the reactor and thereaction is allowed to continue for an additional 30 minutes at whichpoint the mixture is cooled to room temperature. The resultingcore-shell material is precipitated out of the growth solution inside anitrogen atmosphere glovebox by adding a 2:1 mixture of butanol andmethanol. The isolated quantum dots (QDs) are then dissolved in tolueneand precipitated a second time using 2:3 butanol:methanol. The QDs arefinally dispersed in toluene. The isolated material specifications areas follows: Optical Density @ 450 nm=0.316; Abs=501 nm; Emission=518 nm;FWHM=38 nm; Solution QY=60; Film EQE=93%.

EXAMPLE II Coating Core Quantum Dots Using a Coating Process WithoutAmine Species To Produce a Red Emitter

Synthesis of CdSe/ZnS/CdZnS Core-Shell Nanocrystals: In a typicalreaction, red cores with a first absorbance peak at 565 nm (5.19 mL,0.50 mmol Cd) are mixed in a reaction vessel with 1-octadecene (4.63mL), and Zn(Oleate)₂ (0.5 M, 1.68 mL). The reaction vessel is heated to120° C. and vacuum is applied for 15 min. The reaction vessel isback-filled with nitrogen and heated to 310° C. The temperature ramp, isbetween 1° C./5 seconds and 1° C./15 seconds. Once the vessel reaches300° C., octanethiol (0.73 mL) is swiftly injected and a timer isstarted. Once the timer reaches 2 min, one syringe containingZn(Oleate)₂ (0.5 M, 3.26 mL) and Cd(Oleate)₂ (1 M, 2.66 mL), and anothersyringe containing octanethiol (2.74mL) are swiftly injected. Once thetimer reaches 30 min, the heating mantle is dropped and the reactioncooled by subjecting the vessel to a cool air flow. The final materialis precipitated via the addition of butanol (20 mL) and methanol (5 mL),centrifuged at 3000 RCF for 2 min, and the pellet redispersed intohexanes (3 mL). The sample is then precipitated once more via theaddition of butanol (3 mL), and methanol (1 mL), centrifuged, anddispersed into toluene for storage (1.0 g of core/shell material,615-618 nm emission, 25 nm FWHM, >90% EQE in film).

EXAMPLE III

Synthesis of CdSe Cores: The following are added to a 1 L glass reactionvessel: trioctylphosphine oxide (9.69 g), 1-octadecene (ODE, 141.92 g),and 1-octadecylphosphonic acid (1.182g, 3.54 mmol) The vessel issubjected to 3 cycles of vacuum/nitrogen at 120° C., and the temperatureis raised to 270° C. under nitrogen. At 270° C., a solution of 0.25 Mdiisobutylphosphine selenide in trioctylphosphine (DIBP-Se in TOP, 11.03mL, 2.76 mmol), and a solution of 0.25 M cadmium oleate (14.14 mL, 3.54mmol) are rapidly and simultaneously injected, within a period of lessthan 1 second, followed by injection of ODE (76.0 mL) to rapidly dropthe temperature to about 240° C. resulting in the production of quantumdots with an initial absorbance peak between 420-430 nm. 5-20 secondsafter the ODE injection, a solution of Cd(Oleate)₂ (0.5M in a 50/50 v/vmixture of TOP and ODE) is continuously introduced along with a solutionof DIBP-Se (0.45 M in a 50/50 v/v mixture of trioctylphosphine and ODE)at a rate of 11.7 mL/hr. The infusion rate is increased according to thefollowing schedule: 23.3 mL/hr at 15min; 35.0 mL/hr at 25min; 46.7 mL/hrat 35mM; 62.2 mL/hr at 45min; 83.0 mL/hr at 55 min; and 110.6 mL/hr at65min A total of 133.5 mL of each precursor is delivered while thetemperature of the reactor is maintained between 205-240° C. At the endof the infusion, the reaction vessel is cooled rapidly using a flow ofair to bring the temperature down to <150° C. (within 10 min) The finalmaterial is used as is without further purification (First absorbancepeak: 596 nm, Total volume: 553 mL, Reaction yield: 99%). The absorptionspectra for the core is shown in FIG. 1A.

Synthesis of CdSe/ZnSe/CdZnS Core/Shell/Shell): The CdSe coressynthesized as described in the preceding paragraph, with a firstabsorbance peak of 596 nm (42.65 mL, 5 0 mmol Cd), are mixed with1-octadecene (ODE, 60 mL) and Zn(Oleate)₂ (0.5 M, 45.62 mL). Thesolution is degassed at 110° C. for 10 min, and then refilled with N₂.The temperature is set to 320° C., upon which a solution ofdiisobutylphosphine selenide in N-dodecylpyrrolidone (DIBP-Se in NDP,1.0 M, 19.16 mL) mixed with ODE (44.71 mL) is infused at a rate of 186.5mL/hr for 15 min. The temperature is kept between 320-330° C. duringthis infusion stage. At the end of the 15min infusion, the solution isannealed at 320-330° C. for 5min, followed by infusion of the shell 2precursors. The shell 2 precursors include 1) Cd(oleate)₂ (1 M, 31.0 mL)mixed with Zn(oleate)₂ (0.5 M, 119.7 mL), and 2) dodecanethiol (67.3 mL)mixed with ODE (66.9 mL) and TOP (16.7 mL). A total of 150.7 mL of eachprecursor is infused over 30 min. The temperature is kept between315-325° C. during this infusion. At the end of the infusion, thesolution is annealed for 5min at 315-325° C., followed by cooling withan air flow down to <150° C. within 10min. The final core/shell materialis precipitated twice via the addition of butanol and methanol at a 2:1ratio v/v followed by redispersion into toluene for storage (Emission605 nm, FWHM 25 nm, Film EQE at RT: 96%, Film EQE at 140° C.: 96%). Theabsorption spectra for the CdSe/ZnSe/CdZnS quantum dot of this Exampleis shown in FIG. 1B.

EXAMPLE IV Semiconductor Nanocrystals Capable of Emitting Red Light

Synthesis of CdSe Cores: The following are added to a 1L glass reactionvessel: trioctylphosphine oxide (17.10 g), 1-octadecene (181.3 g),1-octadecylphosphonic acid (2.09, 24.95 mmol), and Cd(Oleate)₂ (1 Msolution in trioctylphosphine, 24.95 mL, 24.95 mmol). The vessel issubjected to 3 cycles of vacuum/nitrogen at 120° C., and the temperatureis raised to 270° C. under nitrogen. At 270° C., a solution of 1 Mdiisobutylphosphine selenide in N-dodecylpyrrolidone (DIBP-Se,19.46 mL,19.46 mmol) is rapidly injected, within a period of less than 1 second,followed by injection of 1-octadecene (76.6 mL) to rapidly drop thetemperature to about 240° C. resulting in the production of quantum dotswith an initial absorbance peak between 420-450 nm. 5-20 seconds afterthe ODE quench, a solution of Cd(Oleate)₂ (0.5 M in a 50/50 v/v mixtureof TOP and ODE) is continuously introduced along with a solution ofDIBP-Se (0.4 M in a 60/40 v/v mixture of N-dodecylpyrrolidone and ODE)at a rate of 61.7 mL/hr. At 15 min, the infusion rate is increased to123.4 mL/hr. At 25 min, the infusion rate is increased to 185.2 mL/hour.At 35 min, the infusion rate is increased to 246.9 mL/hr. At 45 min, theinfusion rate is increased to 329.2 mL/hr. A total of 136.8 mL of eachprecursor is delivered while the temperature of the reactor ismaintained between 215-240° C. At the end of the infusion, the reactionvessel is cooled using room temperature airflow over a period of 5-15min. The final material is used as is without further purification(First absorbance peak: 559 nm, Total volume: 587 mL, Reaction yield:99%). The absorption spectrum of the core is shown in FIG. 2A.

Synthesis of CdSe/ZnS/CdZnS Core/Shell/Shell: CdSe cores synthesized asdescribed in the preceding paragraph, with a first absorbance peak of559 nm (72.9 mL, 8 mmol Cd), are mixed with Zn(Oleate)₂ (44.0 mL, 0.5 Min TOP) and 1-octadecene (84.1 mL). The solution is heated to 320° C.,upon which a syringe containing 1-dodecanethiol (39.54 mL) is swiftlyinjected. After 2 min, when the temperature recovers to 310-315° C., theovercoat precursors are delivered via a syringe pump over a period of 30min. The two overcoating precursor stocks include the following: 1)Zn(Oleate)₂ (53.87 mL, 0.5 M in TOP) mixed with Cd(Oleate)₂ (64.64 mL,1.0 M in TOP), and 2) dodecanethiol (33.69 mL) mixed with 1-octadecene(67.86 mL) and TOP (16.96 mL). During the overcoating precursorinfusion, the temperature is kept between 320° C.-330° C. Any volatilesfrom the system are allowed to distill over and leave the system inorder for the temperature to reach 320-330° C. After the infusion ends,the sample is annealed for 5 min at 320-330° C. and cooled to roomtemperature over a period of 5-15 min. The final core/shell material isprecipitated via the addition of butanol and methanol at a 2:1 ratiov/v. The pellet is isolated via centrifugation, and redispersed intotoluene (10 mL) for storage (Emission 598 nm, FWHM 24 nm, Film EQE atRT: 99%, Film EQE at 140° C.: 90-94%). The absorption and emissionspectrum are shown in FIG. 2B.

EXAMPLE V Preparation of Ink Composition & Films

The following describes preparation of an ink formulation includingsemiconductor nanocrystals and preparation of a film from such inkformulation.

EXAMPLE VA Preparation of Ink Formulation

10 mg of semiconductor nanocrystals (inorganic mass as determined viathermal gravimetric analysis (TGA)) in toluene is added to 1.0 mL ofEbecyl 150 and degassed under reduced pressure to remove the toluene andoxygen. Once the toluene is removed, three purge and N₂ back-fill cyclesare completed and then 10 mg of TiO₂ (1% by weight) is added to theformulation and the mixture is degassed under reduced pressure whilestirring in order to disperse the TiO₂. Once these steps are completed,1 drop (˜12 mg) of Irgacure 2022 is added to the formulation and themixture is stirred under air for a few minutes. The formulation is thenready for film preparation.

EXAMPLE VB Preparation of Film

A film prepared from an ink formulation prepared as generally describedin Example VA is prepared as follows. ˜5-10 μL of the formulation isdropped onto a 15 mm diameter borosilicate glass disc (˜230+/−20 μm inthickness). A second 15 mm disk is set on top of the drop of formulationsandwiching the ink between the glass slides. Care is taken to minimizethe amount of ink at the edges that is not completely sandwiched by theglass slides. The sandwich is then brought into a N₂ purge box andinserted into a UV curing station (Dymax 5000-EC Series UV Curing FloodLamp System) and cured with the following curing conditions: Dymax MetalHalide “D” Bulb; Part # 38560; 80-100 milliWatt (mW)/square centimeter(cm²) excitation power with a cure time of 10 seconds. Once the film iscured, the films are then irradiated with 25 mW/cm² of 450 nm LED lightwhile on a hot plate set at 50° C. for 12-18 hrs. (Alternatively, thesamples can be irradiated with approximately 100 mW/cm² of 450 nm LEDlight while on a hot plate set at 80° C. for 1 hour). After thisprocess, the EQE of the film is measured in a QEMS (Labsphere product)integrating sphere system. The films are then ready for temperaturedependent efficiency measurements.

EXAMPLE VC PL vs. Temperature Measurement Protocol

With the room temperature (25° C.) EQE measured in an integrating sphere(Example VB), the sample is then measured on a hotplate at roomtemperature. The measurement involves optically exciting the sample at awavelength shorter than the band edge absorption of the QDs (i.e. 1stexcitonic absorption feature) and collecting both a portion of the PLemission from the sample as well as a portion of the excitation lightafter it interacts with the sample (this light is proportional to theabsorption of the sample). The sample temperature is then raised via thehotplate and equilibrated at an elevated temperature for ˜1 min (thetemperature should not rise slower than 10° C./min) and the sample isthen measured again. This process is repeated for multiple temperaturesbetween 25° C. and about 140° C. or above. Measurements can be atpreselected temperature intervals, e.g., at every 5, 10, or 20 degreeintervals. Other intervals can be selected. The samples are heated andthe measurements taken in the absence of oxygen. For each data point,the sample is held at a given temperature for about <˜1-2 minutes whenPL is measured. The EQE measurements were made using a 440 nm laserlight source. Other adequate light sources include 405 nm laser or blue(405 and 440-450 nm) LED light sources. Monochromatic light from a whitelight monochromator can also be used. The light source should excite thesample with a flux/power density no greater than 100 mW/cm². Preferably,the excitation power density used to measure the sample is lower thanthat used to expose the sample prior to room temperature EQE measurement(as described in preparation of the film, Example VB). The optical pathof the system (both excitation light and emitted semiconductornanocrystal light) is not altered during data collection.

EXAMPLE VI

FIG. 4 graphically depicts the calculated EQE values for the respectivesamples as a function of temperature. The EQE data presented in FIG. 4are calculated based on the integrated PL change with temperature andcorrelated back to the room temperature (RT) EQE for the film. Theintegrated PL at RT is set equal to the RT measured EQE and thereforeany change in PL is then an equivalent % change in EQE with adjustmentfor any absorption change at elevated temperatures.

The PL data shown in FIG. 5 and the EQE data presented in FIG. 4 arebased on sample films prepared with the semiconductor nanocrystals ofthe invention (the film being prepared as generally described in ExampleV) with nanocrystals prepared generally in accordance with the proceduredescribed in Examples III (CdSe/ZnSe/CdZnS—red) and Example IV(CdSe/ZnS/CdZnS—red).

While not wishing to be bound by theory, this illustrates a reduction inthe quenching of semiconductor nanocrystal emission as a function oftemperature (also referred to as “thermal quenching”.)

This result is further illustrated for the same samples in FIG. 6A andFIG. 6B as a normalized integrated plot of absorption versus wavelengthfor semiconductor nanocrystals in accordance with the present invention,prepared generally in accordance with Examples III and IV.

EXAMPLE VII Semiconductor Nanocrystals Capable of Emitting Green LightEXAMPLE VIIA

Synthesis of CdSe Cores (448 nm Target): The following are added to a 1L steel reaction vessel: trioctylphosphine oxide (51.88 g), 1-octadecene(168.46 g), 1-octadecylphosphonic acid (33.09 g, 98.92 mmol), andCd(Oleate)₂ (1M solution in trioctylphosphine, 98.92 mL, 98.92 mmol) Thevessel is subjected to 3 cycles of vacuum/nitrogen at 120° C., and thetemperature is raised to 270° C. under nitrogen. At 270° C., a solutionof 1M diisobutylphosphine selenide in N-dodecylpyrrolidone (DIBP-Se,77.16mL, 77.16 mmol) is rapidly injected, within a period of less than 1second, followed by injection of 1-octadecene (63.5 mL) to rapidly dropthe temperature to about 240° C. resulting in the production of quantumdots with an initial absorbance peak between 420-430 nm. 5-20 secondsafter the ODE injection, a solution of Cd(Oleate)₂ (0.5 M in a 50/50 v/vmixture of TOP and ODE) is continuously introduced along with a solutionof DIBP-Se (0.4 M in a 60/40 v/v mixture of N-dodecylpyrrolidone andODE) at a rate of 29.0 mL/min A total of 74.25 mL of each precursor isdelivered while the temperature of the reactor is maintained between205-240° C. At the end of the infusion, the reaction vessel is cooledrapidly by immersing the reactor in a squalane bath chilled with liquidnitrogen to rapidly bring the temperature down to <150° C. (within 2minutes). The final material is used as is without further purification(First absorbance peak: 448 nm, Total volume: 702 mL, Reaction yield:99%). The absorption spectrum of the core is shown in FIG. 7A.

EXAMPLE VIIB

Synthesis of CdSe/ZnS/CdZnS Core/Shell/Shell: CdSe cores synthesized asdescribed in the preceding paragraph, with a first absorbance peak of448 nm (27.70 mL, 4.78 mmol Cd), are mixed with dodecanethiol (23.76 mL,99.20 mmol) in a syringe. A reaction flask containing Zn(Oleate)₂ (99.20mL, 0.5 M in TOP) is heated to 300° C., upon which the syringecontaining cores and 1-dodecanethiol is swiftly injected. When thetemperature recovers to 310° C. (between 2-8 minutes (min)), theovercoat precursors are delivered via a syringe pump over a period of 32min. The two overcoating precursor stocks include the following: 1)Zn(Oleate)₂ (141.25 mL, 0.5 M in TOP, 70.63 mmol) mixed with Cd(Oleate)₂(79.64 mL, 1.0 M in TOP, 79.64 mmol), and 2) dodecanethiol (39.59 mL,165.29 mmol) mixed 1-octadecene (3.67 mL) and n-trioctylphosphine(0.92mL). During the overcoating precursor infusion, the temperature iskept between 320-330° C. Any volatiles from the system are allowed todistill over and leave the system in order for the temperature to reach320-330° C. After the infusion ends, the sample is annealed for 3minutes at 320-330° C. and cooled to room temperature over a period of5-15 minutes. The final core/shell material is precipitated via theaddition of butanol and methanol at a 2:1 ratio v/v. The pellet isisolated via centrifugation, and redispersed into toluene for storage(Emission 531 nm, FWHM 41 nm, Film EQE at RT: 99%, Film EQE at 140°C.: >90%). The absorption and emission spectra of the resultingovercoated nanocrystals are shown in FIG. 7B.

EXAMPLE VIII Semiconductor Nanocrystals Capable of Emitting Red LightEXAMPLE VIIIA

Synthesis of CdSe Cores: The following are added to a 1L glass reactionvessel: trioctylphosphine oxide (15.42 g), 1-octadecene (ODE, 225.84 g),1-octadecylphosphonic acid (1.88 g, 5.63 mmol) The vessel is subjectedto 3 cycles of vacuum/nitrogen at 120° C., and the temperature is raisedto 270° C. under nitrogen. At 270° C., solutions of 0.25 Mdiisobutylphosphine selenide in N-dodecylpyrrolidone (DIBP-Se, 17.55 mL,4.38 mmol) and 0.25 M Cd(Oleate)₂ in trioctylphosphine/ODE (22.50 mL,5.62 mmol) are rapidly injected, within a period of less than 1 second,followed by injection of ODE (76.0 mL) to rapidly drop the temperatureto about 240° C., resulting in the production of quantum dots with aninitial absorbance peak between 420-450 nm. 5-20 seconds after the ODEquench, a solution of Cd(Oleate)₂ (0.5 M in a 50/50 v/v mixture of TOPand ODE) is continuously introduced along with a solution of DIBP-Se(0.4 M in a 60/40 v/v mixture of N-dodecylpyrrolidone and ODE) at a rateof 55.7 mL/hr. At 15 min, the infusion rate is increased to 111.4 mL/hr.At 25 min, the infusion rate is increased to 167.1 mL/hour. At 35 min,the infusion rate is increased to 222.8 mL/hr. At 45 min, the infusionrate is increased to 297.0 mL/hr. At 55 min, the infusion rate isincreased to 396.0 mL/hr. A total of 149.7 mL of each precursor isdelivered while the temperature of the reactor is maintained between215-240° C. At the end of the infusion, the reaction vessel is cooledusing room temperature airflow over a period of 5-15 min. The finalmaterial is used as is without further purification (First absorbancepeak: 576 nm, total volume: 736.5 mL, Reaction yield: 99%). Theabsorption spectrum of the core is shown in FIG. 8A.

EXAMPLE VIIIB

Synthesis of CdSe/ZnS/CdZnS Core/Shell/Shell: CdSe cores synthesized asdescribed in the preceding paragraph, with a first absorbance peak of576 nm (90.10 mL, 8.70 mmol Cd), are mixed with Zn(Oleate)₂ (47.62 mL,0.5 M in TOP, 23.81 mmol). The solution is heated to 320° C., upon whicha syringe containing 1-dodecanethiol (8.55 mL, 35.7 mmol) is swiftlyinjected. After 10 min of annealing between 305-325° C., the overcoatprecursors are delivered via a syringe pump over a period of 30 min. Thetwo overcoating precursor stocks include the following: 1) Zn(Oleate)₂(89.73 mL, 0.5 M in TOP, 44.87 mmol) mixed with Cd(Oleate)₂ (104.68 mL,1.0 M in TOP, 104.68 mmol), and 2) dodecanethiol (70.59 mL, 294.70 mmol)mixed with 1-octadecene (21.29 mL) and TOP (5.32 mL). During theovercoating precursor infusion, the temperature is kept between 320-330°C. Any volatiles from the system are allowed to distill over and leavethe system in order for the temperature to reach 320-330° C. After theinfusion ends, the sample is annealed for 5 min at 320-330° C. andcooled to room temperature over a period of 5-15 min. The finalcore/shell material is precipitated via the addition of butanol andmethanol at a 2:1 ratio v/v. The pellet is isolated via centrifugation,and redispersed into toluene (200mL) for storage (Emission 617 nm, FWHM30 nm, Film EQE at RT: 92%, Film EQE at 140° C.: 75-80%). The absorptionand emission spectra of the resulting overcoated nanocrystals are shownin FIG. 8B.

For assessing the EQE vs. temperature response of a semiconductornanocrystal sample, a relative EQE measurement can be performed wherebythe ρPL values can be correlated back to the room temperature orstarting EQE (EQE can be measured using DeMello's method in anintegrating sphere). In other words, the ΣPL at room temp is set equalto the room temp EQE, and then the % drop in ΣPL at elevatedtemperatures, equates to an equivalent % drop from the room temperatureEQE value. ΣPL at RT is also referred to herein as Io, and ΣPL attemperature T is also referred to herein as I(T).)

“Solid state external quantum efficiency” (also referred to herein as“EQE” or “solid state photoluminescent efficiency) can be measured in a12” integrating sphere using a NIST traceable calibrated light source,using the method developed by Mello et al., Advanced Materials 9(3):230(1997), which is hereby incorporated by reference. Such measurements canalso be made with a QEMS from LabSphere (which utilizes a 4 in sphere;e.g. QEMS-2000: World Wide Websitelaser2000.nl/upload/documenten/fop_(—)21-en2.pdf).

As used herein, the singular forms “a”, “an” and “the” include pluralunless the context clearly dictates otherwise. Thus, for example,reference to an emissive material includes reference to one or more ofsuch materials.

Applicants specifically incorporate the entire contents of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the present specification andpractice of the present invention disclosed herein. It is intended thatthe present specification and examples be considered as exemplary onlywith a true scope and spirit of the invention being indicated by thefollowing claims and equivalents thereof.

Although the subject matter has been described in language specific tostructural features and/or methodological acts, it is to be understoodthat the subject matter defined in the appended claims is notnecessarily limited to the specific features or acts described above.Rather, the specific features and acts described above are disclosed asexample forms of implementing the claims.

1-36. (canceled)
 37. A method of making quantum dots having a coatingthereon comprising: providing a first reaction mixture comprising corequantum dots, a zinc carboxylate and a chalcogen source at a temperatureof greater than 240° C. in the substantial absence of an amine species;forming a first coating on the core quantum dots from the zinccarboxylate and chalcogen source to form first coated quantum dots;providing a second reaction mixture comprising one or more metalcarboxylates and one or more chalcogenide sources with the first coatedquantum dots at a temperature of greater than 240° C. in the substantialabsence of an amine species; and forming a second coating on the firstcoated quantum dots from the one or metal carboxylates and the one ormore chalcogenide sources.
 38. A method in accordance with claim 37wherein the temperature of the first reaction mixture is greater than280° C.
 39. A method in accordance with claim 37 wherein the temperatureof the second reaction mixture is greater than 280° C.
 40. The method ofclaim 37 wherein the core quantum dots comprise a Group II-VIsemiconductor material.
 41. The method of claim 37 wherein a firstcoating comprising one or more zinc chalcogenides is formed on the corequantum dots in the absence of amine species.
 42. The method of claim 37wherein the second coating comprises Cd_(X)Zn_(1-X)S wherein 0<x<1. 43.The method of claim 37 wherein the core quantum dots comprise CdSe. 44.Quantum dots comprising a quantum dot core with a first coatingcomprising zinc chalcogenide on an outer surface of the quantum dot coreand an outermost coating comprising a semiconductor material, whereinthe outermost coating is substantially free of amine species.
 45. Thequantum dots of claim 44 wherein the outermost coating comprises asemiconductor material comprising Cd_(X)Zn_(1-X)S wherein 0<x<1. 46-49.(canceled)
 50. A composition comprising a host material and quantum dotsin accordance with claim 44 wherein the host material has reduceddiscoloration upon exposure to light flux in excess of 1 W/cm² and/or atemperature >100° C. compared to a control composition comprising thehost material and control quantum dots including an amine speciesassociated with an outermost surface of the control quantum dots. 51.The composition of claim 50 wherein the host material comprises apolymer matrix.
 52. A quantum dot prepared by a method in accordancewith claim 37 wherein the quantum dot has a solid state EQE of at least90%. 53-113. (canceled)
 114. The method of claim 37 wherein thechalcogen source comprises a sulfur source.
 115. The method of claim 114wherein the temperature of the first reaction mixture is at least about270° C.
 116. The method of claim 114 wherein the temperature of thefirst reaction mixture is at least about 300° C.,
 117. The method ofclaim 114 wherein the temperature of the first reaction mixture isgreater than 310° C.
 118. The method of claim 37 wherein the chalcogensource comprises a selenium source.
 119. The method of claim 118 whereinthe temperature of the first reaction mixture is at least about 300° C.120. The method of claim 118 wherein the temperature of the firstreaction mixture is greater than 310° C.
 121. Quantum dots in accordancewith claim 44 wherein the quantum dot core comprises cadmium andselenium and the outermost coating comprises a semiconductor materialcomprising Cd_(X)Zn_(1-X)S wherein 0<x<1.